Nas últimas décadas o crescimento industrial decorrente do desenvolvimento tecnológico e outras atividades consideradas indispensáveis à vida humana, estão gerando graves problemas ambientais, que está despertando uma preocupação a nível mundial. Dentre os vários contaminantes os metais tóxicos têm recebido atenção especial, pela sua persistência ao ingressar nos ecossistemas acumulando-se por toda a cadeia alimentar, uma vez que são extremamente tóxicos, mesmo em quantidades muito baixas. No Brasil, a legislação ambiental vigente já estabelece normas bastante rigorosas no que diz respeito ao descarte de águas contaminadas por metais tóxicos. Para que o tratamento deste tipo de efluentes seja feito adequadamente, e para que possam ser impostos limites máximos cada vez mais compatíveis com a sustentabilidade da vida moderna, torna-se relevante a preocupação com novas tecnologias mais eficientes e econômicas que permitam a remoção de metais tóxicos do ambiente contaminado. Hoje o tratamento do ambiente contaminado é realizado empregandose tecnologias convencionais baseadas em princípios físico-químicos, as quais estão sendo consideradas ineficientes e economicamente inviáveis. Alternativamente, uma nova tecnologia, a biorremediação, vem ganhando cada vez mais importância, devido às vantagens que oferece: simplicidade, eficiência e baixo custo. Para isto é necessário ser avaliada a utilização de microorganismos resistentes e eficazes na remoção do metal, pois, nesta fase são necessários que sejam selecionados organismos com características favoráveis ao processo. Dentro deste contexto, a proposta desse projeto foi isolar e caracterizar micro-organismos de uma área de mineração, avaliando os mecanismos e estratégias para o seu uso na remediação de áreas contaminadas a fim de otimizar a sua capacidade de adsorver íons de metais tóxicos, com vistas à utilização destas bactérias para a biossorção de efluentes de mineração. Foram isoladas e identificadas 105 cepas resistentes a cobre, destas 12 cepas foram capazes de crescer à 7.5 mM de cobre. Experimentos de adsorção com metais tóxicos (Cu, Cd e Ni) mostraram que tais cepas são promissoras na ampliação de tecnologias para uma mineração menos impactante, como a exploração de fontes de metais em baixa concentração, transformando o resíduo em fonte de extração economicamente viável e ambientalmente favorável. / Recently, technological development has been resulted in an industrial growth and has been creating serious environmental problems as concern worldwide. Toxic metals have received special attention among many others contaminants, because their persistence in ecosystems and their capability of accumulation throughout the food chain (even in low amounts). Environmental legislation in Brazil has very strict standards regarding discharge of toxic metals contaminated water. For a successful treatment of such effluents, it is relevant to concern about new technologies more efficient and economics to allow the removal of metals heavy from contaminated environment. Today the treatment of contaminated area is carried out conventional technologies based on physicochemical principles, which are inefficient and uneconomical. Alternatively, a new technology, called bioremediation, is being more important due to the advantages it offers: simplicity, efficiency and low cost. Bioremediation may be a viable alternative for areas contaminated by toxic metals. It\'s needed to evaluate the use of resistant and effective microorganisms in removing the metal, because it\'s required to be selected organisms with favorable characteristics for the process. In this context, the aim of this project is isolating and characterizing microorganisms from a mining area, evaluating the mechanisms and strategies for using in the remediation of contaminated areas, in order to optimize its adsorb heavy metal ions ability and use these bacteria for bioremediation of mining effluents. This work isolated and identified 105 strains resistant to copper, 12 of them were able to grow up to 7.5 mM copper, adsorption experiments with toxic metals (Cu, Cd and Ni) showed that these strains are promising in expanding technologies for sustainable mining, such as the exploitation of low concentration metal sources, turning waste into economically viable mining and environmentally friendly.

Prefabricated baby food is under strict EU legislation by Commission Regulation (EC) 1881/2006 Setting maximum levels for certain contaminants in foodstuffs regarding the maximum allowed content of potentially harmful elements. For potentially toxic trace elements the regulated maximum content is regulated for lead, cadmium, mercury, inorganic tin, inorganic arsenic, cesium, copper and manganese. The Swedish national food agency (Livsmedelsverket) conducts chemical analyses of the regulated elements by full microwave acid digestion followed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) analysis. In this study a simple artificial in vitro digestion method was developed using a commercially available enzyme supplement and optimized to determine the bio-accessible amount of eight potentially harmful metal trace elements that are associated with modern electronics (lithium, vanadium, cobalt, nickel, arsenic, selenium, cadmium and lead) in five prefabricated baby meals from the Swedish market by well-established manufacturers. The results were compared to the total mass content as well as the regulated limits and toxicological literature data. The samples had analyte dry mass contents that were extractable by the developed in vitro method that ranged from 0.0314 μg g-1 to 0.0691 μg g-1 for lithium, 9.42*10-5 μg g-1 to 0.0152 μg g-1 for vanadium, 6.61*10-3 μg g-1 to 30.9*10-3 μg g-1 for cobalt, 0.0599 μg g-1 to 0.194 μg g-1 for nickel, 4.54*10-4 μg g-1 to 0.0431 μg g-1 for arsenic, 8.87*10-4 μg g-1 to 9.85*10-3 μg g-1 for cadmium and 1.24*10-3 μg g-1 to 0.0232 μg g-1 for lead. Selenium was not detected in any of the samples. None of the samples were found to contain toxic levels of any of the quantified elements. Comparisons and paired t-tests of recoveries between the in vitro digestion and control procedures consisting of digestion solutions that exclude either enzymes, pH adjustment or both suggested that lithium, cobalt and cadmium were protein bound and that the digestion enzymes used had a statistically significant effected on the recovery. With further optimization and more extensive comparison to reference data the method could potentially be established as a simple and affordable alternative to more elaborate methods for screening or small scale analysis of the bio-accessible fraction of metal trace elements in food.

Ce travail concerne la synthèse, les études des propriétés photophysiques et de complexation des molécules fluorescentes pour la détection sélective de cations toxiques tels que le césium, l'uranyle et l'arsenic. Tout d'abord, deux nouveaux capteurs fluorescents pour le césium, Calix-COU-P et Calix-COU-Benz-CN, comportant le Calix[4]arène-couronne-6 et le fluorophore coumarine ont été synthétisés avec succès. En ce qui concerne le Calix-COU-P, une forte exaltation de fluorescence et un déplacement bathochrome d'absorption ont été observés en présence de césium dans l'eau. Une très bonne limite de détection (0,77 μM) ainsi qu'une excellente sélectivité vis-à-vis du césium ont été observées, démontrant que Calix-COU-P pourrait être un capteur exceptionnel pour la détection de césium dans l'eau. Calix-COU-Benz-CN possède quant à lui des propriétés photophysiques prometteuses dans un milieu partiellement aqueux avec des bandes d'absorption et de fluorescence intenses en visible grâce à la présence des groupements benzothiazole et cyano. L'addition de césium conduit aux déplacements ver le bleu des spectres d'absorption et une augmentation de l'intensité de fluorescence. L'étude de la cinétique de complexation entre Calix-COU-Benz-CN et Cs+ par la technique « stopped-flow » a montré une cinétique rapide à faibles concentrations de cations et une cinétique plus longue à des concentrations élevées (> 10 mM). Calix-COU-Benz-CN a ensuite été incorporé dans un dispositif microfluidique. Une courbe d'étalonnage qui représente l'intensité de fluorescence en fonction de la concentration du césium montre une valeur de limite de détection de l’ordre de 2,0 μM. Deux composés analogues contenant la même entité complexante Calix[4]arène-couronne-6 ont été également synthétisés et greffés sur des nanoparticules magnétiques afin d’obtenir un matériau fonctionnalisé pour la décontamination de l’eau contenant le césium radioactif. L'étude préliminaire montre que les nanoparticules fonctionnalisées pourraient capter efficacement une quantité très faible du césium dans l’eau contaminée. Par la suite, en vue de développer des capteurs pour l’uranyle, une série de dérivés de salicylaldéhyde-azine ont été synthétisés et caractérisés. Leurs propriétés d'émission induites par l'agrégation (AIE) ont été étudiées. Dans un mélange eau/acétonitrile, les composés U1 et U2 présentent une forte fluorescence lors de l'agrégation tandis que le composé U3 ne présente pas cet effet AIE dans la même condition. Grâce aux sites de complexation contenant des atomes d’oxygène et d'azote, ces molécules présentent une complexation efficace avec les ions uranyle et induire une extinction de la fluorescence. Dans notre étude, il était intéressant de noter la présence d’uranyle conduit à une destruction de l'agrégation, en particulier pour la molécule U2 dans un mélange eau / acétonitrile 60:40. L’extinction de l’émission a été expliquée par des processus de destruction d'agrégats émissifs lors de la complexation avec le cation. Le mécanisme proposé a été validé par des expériences de diffusion dynamique de la lumière et de microscopie électronique à balayage. Le composé U2 présente une bonne sélectivité vis-à-vis de l'uranyle en présence des lanthanides et des autres cations compétitifs. Le capteur permet la détection de concentrations de l’ordre ppb en uranyle. Enfin, la synthèse et l'étude de nouveaux capteurs pour la détection de l’arsenic ont également été discutées. Une série de capteurs fluorescents portant l’entité complexante cystéine a été synthétisée et leurs propriétés complexantes pour l'arsenic ont été étudiées. De plus, des nanoparticules d'or modifiées par la cystéine, le glutathion et le dithiothréitol ont été synthétisées. La complexation de l'ion arsenic avec ces nanoparticules a été étudiée et discutée. Une perspective sur le développement de nouveaux capteurs pour l’arsenic a été proposée. / This thesis focuses on the synthesis, photophysical and complexation studies of fluorescent molecules for the selective detection of toxic cations such as cesium, uranyl and arsenic. Firstly, two new fluorescent sensors Calix-COU-P and Calix-COU-Benz-CN for cesium cations based on Calix[4]arene-crown-6 and coumarin fluorophore were successfully synthesized. For Calix-COU-P, a remarkable fluorescence enhancement and a red shift in absorption were observed due to the complexation with cesium cation in water. Good detection limits (0.77 µM) together with an excellent selectivity towards cesium were observed, demonstrating that Calix-COU-P could be an outstanding sensor for the detection of cesium cation in water. Calix-COU-Benz-CN possesses exceptional photophysical properties in an organoaqueous solution with intense visible absorption and emission bands thanks to benzothiazole and cyano groups. The addition of cesium cation to Calix-COU-Benz-CN offered noticeable blue shifts of the absorption spectra and considerably enhanced the emission intensity. The kinetic study of the complexation between Calix-COU-Benz-CN and Cs+ by stopped-flow experiments showed a rapid kinetic at small concentrations of cations and a lower kinetic at higher concentrations (> 10 mM). Calix-COU-Benz-CN was then incorporated into a microfluidic device. The voltage signals, which are proportional to the fluorescence intensity, were monitored continuously at various cesium concentrations. A calibration curve which represents the fluorescence intensity as a function of cesium cation concentration gives a value of detection limit up to 2.0 µM. This value is only slightly higher than the detection limit obtained by fluorescence titration (1.67 µM), which suggests that the microfluidic device is capable to provide good sensitivity towards targeted ion for real-world applications. Furthermore, two analogous compounds Calix-DOP and Calix-DOP-P containing the same complexing entity were also synthesized and grafted onto magnetic nanoparticles in order to obtain a functionalized material for the decontamination of the water containing radioactive cesium. The preliminary study shows that functionalized nanoparticles could efficiently sequester cesium ions from contaminated water.Afterward, to develop new sensors for the detection of uranyl cations, a series of salicylaldehyde azine derivatives have been synthesized and characterized. Their aggregation induced emission properties were studied. In water/acetonitrile solvent, compounds U1 and U2 exhibited strong fluorescence upon aggregation while compound U3 did not aggregate and stayed in solution as well-dispersed molecules. Owning to oxygen and nitrogen binding sites, the molecules could complex uranyl ions and induced fluorescence quenching. In our study, it was interesting to understand that the effect of uranyl was somewhat more destructive rather than constructive to the aggregation. The most obvious quenching effect was observed for the aggregates of U2 in water/acetonitrile 60:40. The emission quenching was explained by aggregate-breaking processes, that the emitting aggregates could be destroyed by the complexation with uranyl cation. The proposed mechanism was further supported by dynamic light scattering and scanning electron microscope experiments. Compound U2 showed good selectivity towards uranyl over lanthanides and other common cations. The sensor could detect uranyl up to ppb scale.Finally, synthesis and studies of new sensors for the detection of arsenic ion were also discussed. A series of fluorescent sensors bearing cysteine moiety was synthesized and their complexing properties for arsenic were studied. Furthermore, gold nanoparticles which were modified by cysteine, glutathione and dithiothreitol were synthesized. The complexation of arsenic ion with these modified gold nanoparticles was studied and discussed. A perspective for further development of arsenic sensors was proposed.

No description available.

Harmattan and Dust (sand) storms together with anthropogenic activities including the use of firewood and kerosene as fuel for cooking, and diesel/petrol generators for electricity generation are potential sources of particulate and gaseous pollutants in homes in Damaturu town, Nigeria. Other activities like the burning of locally produced incense and mosquito coils as well as the use of aerosol sprays are further possible sources of indoor pollution, which may result in exposure of people to a range of pollutants through inhalation, by ingestion of settled dusts as well as dermal contact. Local people associate occurrence of dust events with adverse health effects and hence there is a need for an understanding of the composition of the settled and airborne dusts in order to assess the possible associated health risks. The first phase of the study involved selection and development of methods of dust sampling and analysis. For validation of the methods employed and to establish a broad understanding of the characteristics of the settled dusts, an initial survey study was conducted involving the application of thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS) analysis for organic compound analysis, scanning electron microscopy (SEM), inductively coupled plasma-mass spectrometry (ICP-MS) for analysis of metals, and microbiological analysis. Airborne samples were also collected using sorbent tubes to determine organic compounds in air during activities such as cooking with kerosene, gas, and firewood as well as during electricity generation with fossil fuels. Carbon monoxide (CO) and ultrafine particles (UFPs) monitored simultaneously during some of the household activities. The study involved a novel method of extracting organic chemical emissions from dust by heating of the dusts directly in a micro chamber (μ-CTETM) and collection of emissions on sampling tubes. The method provided a relatively quick way of collecting chemical emissions from dusts that are readily available for release. The sampled tubes were analysed by TD/GC/MS. The conventional solvent extraction of the dusts was also carried out and the extracts were analysed by liquid injection-GC/MS and results of the two methods compared. The study determined a number of constituents (metals, SVOCs, phthalates and physical properties) of dusts collected from households in Damaturu during different weather events and from different indoor/outdoor locations; and compared with some UK samples. The samples investigated include dusts deposited; during two notable dusty-weather events (Harmattan and Storm) as well as when there was no notable dust event; during human activities; and dusts from different types of buildings (modern and traditional homes) as well as inside and outside homes. A standard reference material for organic chemicals (SRM 2585) was also analysed. The physical characterization of the settled house dust samples analysed revealed the various shapes and sizes, and elemental composition of the constituents, which included respirable particles. The microbial analysis also indicated the presence of the spores of a host of fungi and bacterial species; and the possible contributions of household activities to the increased production of pollutants (UFP and CO) ascertained. The μ-CTE extraction of the house dusts by heating with TD/GC/MS analysis of the emissions as well as the solvent extraction-GC/MS revealed the presence of many organic chemical compounds with different analytical retention times and varying concentrations in the dust samples. Chemicals of interest quantified: benzene, hexanal, nonanal, diethyl phthalate (DEP), diisobutylphthalate (DIBP), dibutylphthalate (DBP), and diethylhexylphthalate (DEHP). A host of other chemicals commonly present in the analysed samples identified using the NIST library associated with the MS system software. These chemicals included naphthalene and C10-C16 aliphatic and aromatic hydrocarbons, which would need confirmation by running the pure compound samples. There was an observed higher concentration of the chemicals in the solvent extracts than the μ-CTE extracted dust. The higher concentration of the chemicals in the solvent extracts expected due to the aggressive removal of the chemicals by the organic solvent whereas in the case of thermal extraction only the readily available chemicals (loosely bound to the matrix) released by increases in temperature were removed. Generally, the concentrations of the chemicals found were higher in the indoor than in the outdoor dust samples. In the analysis of the dusts collected during weather events; higher chemical concentrations observed in the samples collected during Harmattan period than the other periods. The Harmattan dust period may pose increased exposures to dust and possible health risks. More exposure is expected to occur in the traditional homes compared with the modern homes due to the higher concentrations of the chemicals in both the indoors and the outdoors and this may be especially important to women and children who spend most of their times at home. Metal analysis involved microwave-assisted digestion of the dust samples followed by ICP-MS analysis. The total quant method of metal analysis for a general profiling indicated the presence of more than 50 elemental contaminants in house dust. The results of the quantitative analysis for six target metals: Cd, Cr, Cu, Ni, Pb, and Zn showed their presence in all indoor and the outdoor dust samples. The mean concentrations showed that the metals were in higher concentrations in the indoor dusts than in the outdoor dusts. The quantitative analysis carried out indicated higher metal contents in the storm dusts than the dusts during the other periods. Results of the dusts collected from modern and traditional homes indicated the presence of the metals in higher concentrations in the dusts from traditional homes than the dusts from the modern homes. The estimated mean concentrations of the metals and phthalates inadvertently ingested as a constituent of dust indicated that some of the pollutants could exceed the tolerable daily intake (TDI) due to high exposures to dust expected to be the case in Damaturu. The results of the investigation of the dust composition, combined with information on exposure to dust and pollutants, show that dusts are a risk to the health of people in the Damataru community. Recommendations are made for more studies to provide a better understanding of dust ingestion and exposure to some phthalates and heavy metals in particular and the possible health risks. To the best of my knowledge, this is the first ever research study of airborne and settled dusts undertaken in North-Eastern Nigeria.

The Vůznice Reservoir is located in the Protected Landscape Area Křivoklátsko. The thesis took advantage of the special possibilities to sample bottom sediment from the drained reservoir's space. The Vůznice Reservoir is discharged only exceptionally. Concentrations of heavy metals were evaluated in the sediments' samples. Given values were compared with pollution limits under current legislation of the Czech Republic for possible application of sediments on agricultural land resources. In addition, the values were compared with the U.S. EPA limits, particularly with PEC and TEC. Selected heavy metals meet the required limits of Decree No. 257/2009 Coll. placed on the sediment. Key words: toxic metals, Vuznice, bottom sediment, application of dredged sediments on land

Diariamente milhares de profissionais da área de segurança utilizam armas de fogo, quer em ações de combate a criminalidade; quer em treinamentos obrigatórios que a atividade exige. Apesar disso a quantidade de informação sobre os riscos à saúde desses profissionais devido da exposição aos resíduos de disparos, especialmente quando são usadas armas de grosso calibre, ainda é escassa. Este trabalho pretendeu trazer uma contribuição às discussões sobre o tema com uma proposta de normalização para ser observada no planejamento dos procedimentos de treinamento e atividades desses profissionais. Para tanto foram estudados dois grupos de profissionais: o primeiro, profissionais militares da Polícia Militar do Estado de São Paulo durante intensas jornadas de treinamento com esforço físico e grande numero de disparos com armas de fogo de grosso calibre O segundo grupo envolvendo peritos criminais do núcleo de balística do Instituto de Criminalística da Secretaria de Segurança do Estado de São Paulo. Foram utilizadas amostras de materiais biológicos (sangue, urina e saliva) e amostras do ar dos ambientes fechados onde estas rotinas de trabalho ocorrem. No caso dos profissionais militares, os níveis dos metais monitorados no ar variaram de acordo com o tipo de arma e munição utilizada, sendo ultrapassado o limite de tolerância estabelecido na NR-15 (100 μg/m3) após o uso de espingarda (216 μg/m3). A média e desvio padrão dos níveis de chumbo no sangue antes (3,3 μg/dL ± 0,7) e depois (18,2 μg/dL ± 5,1) do curso indicam que ouve um aumento importante num curto período de tempo, também houve aumento nos níveis de chumbo e antimônio na urina. No segundo caso de exposição ocupacional aos resíduos de disparo no núcleo dos peritos balísticos se verificou uma baixa quantidade de resíduos no ambiente de trabalho, se comparado com o Limite de Tolerância preconizado na norma NR-15, e uma baixa quantidade de chumbo no sangue (3,9 μg/dL ± 0,8) se comparado com o Índice Biológico Maximo Permitido IBMP (60 μg/dL) estabelecido na NR-7, sem embargo quando comparado o grupo de balísticos com o grupo controle (1,8 μg/dL ± 0,7) estabeleceu se uma diferença. O estudo dos cenários de exposição permitiu gerar uma proposta para trabalho seguro nestes ambientes e recomendações para o desenho e uso de estantes fechados de disparo. Os câmbios que se introduzam nos costumes e comportamentos dos profissionais levaram uma diminuição do risco associado ao uso de armas de fogo nestes estantes. As conclusões do presente trabalho contribuem para a adequação das medidas de proteção dos trabalhadores de segurança, e na adequação da legislação relativa aos limites de tolerância e índices bilógicos empregados no controle de saúde ocupacional. / Daily thousands of military officers from security forces use fire arms, sometimes in actions against crime or in mandatory training seasons. Despite of this, there is a few information about the risk associated with firing ranges, especially when heavy weapons are used in a hard training seasons with hard physical work and elevated number of rounds, the security forces might be under risk of intoxication. Other types of exposure with less frequency and intensity, but using a high lead containing ammunition and different types of weapons, like in the ballistics forensic cases are not yet sufficiently studied. Data from these types of occupational exposure in these environments are important in order to establish safety working procedures. The goal in this research is to study the occupational exposure in the police department and the ballistics laboratories in personal who are under the risk of this exposure in their routinely daily work and during the training courses in the Sao Paulo´s Military Police Department. In order to reach this, some biological materials were sampled (blood, urine and saliva) as well as air samples from the environment in the firing ranges during routinely daily work. In the two studied cases the monitored airborne lead varied in accordance with the type of weapon and ammunition used, and was ultra passed the limit of exposure established in the norm NR-15 (100 μg/m3) after the shot gun was used during the training season (216 μg/m3). The average and standard deviation of lead content in blood before (3,3 μg/dL ± 0,7) and after (18,2 μg/dL ± 5,1) de training season shows a significant rise of the lead levels in a very short period of time. An increment of the lead and antimony levels in urine was demonstrated. The other studied case, in the ballistics laboratory showed minor increments of lead in blood and airborne residues when compared with the limits established in the norm NR- 7 (60 μg/dL) but when compared in a cohort study the data lead to establish a significant difference between the exposed group from the ballistics and the control group. These results let us to design a proposal to safely work in these environments and to give the recommendations in the engineering design of the indoor ranges. The implemented changes will lead to minimize the risk associated with the use of weapons and lead containing ammunitions. The conclusions of the present work contribute to adequateness of the related legislation and the tolerance limits of exposure used in the occupational health practice.

No Brasil, populações ribeirinhas da Amazônia estão expostas ao metilmercúrio (MeHg) e ao chumbo (Pb) oriundos, respectivamente, de peixes e farinha de mandioca contaminados. Embora a toxicidade destes elementos químicos seja explorada há tempo, pouco se sabe sobre os efeitos decorrentes da exposição crônica a baixas doses destes toxicantes e, menos ainda, acerca da exposição simultânea a estes dois metais. Neste sentido, este trabalho foi desenvolvido objetivando avaliar a ocorrência de efeitos bioquímicos, genotóxicos e relacionados ao estresse oxidativo, decorrentes da exposição crônica de ratos a baixas doses de MeHg e Pb, associados ou não, bem como a distribuição tecidual destes metais. Adicionalmente, foram investigados os efeitos da administração da vitamina antioxidante niacina (NA) diante destas exposições. Para isto, ratos machos Wistar foram divididos em 8 grupos (n = 6): Grupo controle; Grupo MeHg, tratado com cloreto de MeHg (140 ?g/Kg/dia) por gavagem; Grupo Pb, tratado com acetato de Pb (648 ?g/Kg/dia) por gavagem; Grupo MeHg + Pb, tratado com MeHg (140 ?g/Kg/dia) e Pb (648 ?g/Kg/dia) por gavagem. Grupos paralelos (NA; NA + MeHg; NA + Pb e NA + MeHg + Pb) receberam o mesmo tratamento associado à suplementação de niacina (50 mg/Kg/dia) adicionada na água. O tratamento teve duração de 92 dias. Foram avaliados os parâmetros bioquímicos colesterol total e frações, glicose, atividade das enzimas hepáticas aspartato aminotransferase (AST) e alanina aminotransferase (ALT), e hemoglobina. Os marcadores relacionados ao estresse oxidativo determinados foram tióis totais (GSH); lipoperoxidação, avaliada pela concentração de malondialdeído (MDA) e espécies reativas ao ácido barbitúrico (TBARS); além da atividade das enzimas antioxidantes superóxido dismutase (SOD), glutationa peroxidase (GSH-Px) e catalase (CAT). Ainda, foi avaliada a concentração de óxido nítrico (NO) plasmático e a genotoxicidade por meio do Ensaio Cometa. As concentrações de mercúrio (Hg) e Pb foram determinadas em sangue total e tecidos dos animais por ICP-MS. A exposição a baixas doses de MeHg causou genotoxicidade, redução na atividade da CAT no cérebro e nas concentrações de GSH no sangue e fígado dos animais, além de peroxidação lipídica, evidenciada pelo aumento nas concentrações de MDA e TBARS no plasma e cérebro dos ratos. Os animais expostos exclusivamente ao MeHg apresentaram ainda atividade de ALT aumentada e concentração plasmática de NO reduzida. A distribuição do Hg no organismo foi maior no rim, seguido por sangue e, posteriormente, cérebro. A exposição exclusivamente ao Pb promoveu redução na concentração de GSH e na atividade de CAT, além de induzir peroxidação lipídica no cérebro dos ratos. A exposição ao Pb também resultou em genotoxicidade, além de redução na concentração de hemoglobina e NO. As maiores concentrações de Pb foram observadas no osso (fêmur) > rim > cérebro > sangue. A exposição simultânea ao MeHg e Pb não resultou em sinergismo de efeitos tóxicos em comparação ao tratamento com os metais individualmente. Considerando parâmetros como concentração plasmática de NO e GSH no sangue, fígado e cérebro, a exposição ii conjunta aos metais antagonizou os efeitos desencadeados por cada metal individualmente. Entretanto, a coexposição MeHg/Pb também promoveu genotoxicidade e lipoperoxidação. Já a administração de niacina apresentou efeitos protetores frente às alterações desencadeadas pela exposição aos metais, sem alterar a concentração e distribuição destes nos órgãos/tecidos. Em resumo, nossos resultados mostram que a exposição ao MeHg e Pb, até mesmo em doses baixas, induz toxicidade em roedores. Visto que a niacina apresentou efeitos antioxidantes e antigenotóxicos relevantes, a suplementação com esta vitamina pode ser uma alternativa para amenizar os efeitos tóxicos decorrentes da exposição ao MeHg e/ou Pb. / In Brazil, riverside populations of the Amazon are exposed to methylmercury (MeHg) and lead (Pb) coming respectively from contaminated fish and cassava flour. Although the toxicity of these elements has been explored for some time, little is known about the effects of chronic exposure at low doses and even less about the simultaneous exposure. Thus, this work aimed to evaluate the occurrence of biochemical, genotoxic and oxidative stress related effects, resulting from chronic exposure of rats at low doses of MeHg and Pb, associated or not, as well as the tissue distribution of these elements. Additionally, the effects of co-administration of the antioxidant vitamin niacin (NA) on the toxic effects were investigated. For this, male Wistar rats were divided into 8 groups (n = 6): Control group; MeHg group, received MeHg chloride (140 ?g/Kg/day) by gavage; Pb group, received Pb acetate (648 ?g/Kg/day) by gavage; MeHg + Pb group, received MeHg (140 ?g/Kg/day) and Pb (648 ?g/Kg/day) by gavage. Parallel groups (NA; NA + MeHg; NA + Pb and NA + MeHg + Pb) received the same treatment associated with niacin supplementation (50 mg/kg/day) added to the water. The treatment lasted 92 days. Biochemical parameters such as total and fractions cholesterol, glucose, hepatic enzyme activity such as aspartate transaminase (AST) and alanine transaminase (ALT), and hemoglobin were determined. Oxidative stress markers such as total thiols (GSH); lipid peroxidation, measured by malondialdehyde (MDA) and thiobarbituric acid reactive substances (TBARS) concentrations; besides the activity of superoxide dismutase (SOD), glutathione peroxidase (GSH-Px) and catalase (CAT) antioxidant enzymes were evaluated in treated and non-treated animals. Also, the concentration of plasmatic nitric oxide (NO) and genotoxicity by the Comet Assay was assessed. Levels of mercury (Hg) and Pb were determined in whole blood and tissues of animals by ICP-MS. Low doses of exposure to MeHg caused reduction of CAT activity in the brain and reduction of GSH concentrations in the blood and liver of animals, besides genotoxicity and lipid peroxidation, as evidenced by the increase levels of MDA and TBARS in plasma and brain of rats. Animals exposed to MeHg still had increased ALT activity and decreased plasmatic NO levels. Levels of Hg were found higher in kidney, followed by blood and brain. Pb exposure alone promoted reduction of GSH concentration and CAT activity, and induced lipid peroxidation in the brain of rats. Moreover, genotoxicity, and reduction of hemoglobin and plasmatic NO levels were also observed in the group of animals treated only with Pb. The highest Pb levels were observed in bone (femur) > kidney > brain > blood. Simultaneous exposure to MeHg and Pb did not result in synergistic toxic effects. Considering parameters such as plasmatic NO and GSH levels in blood, liver and brain, the joint exposure to metals antagonized the effects produced by each metal individually. However, the MeHg/Pb co-exposure also promoted genotoxicity and lipid peroxidation. On the other hand, administration of niacin exhibited protective effects under the changes triggered by exposure to metals without altering the concentration and distribution of these metals in the organs/tissues of animals. Taken together, our results demonstrated that exposure to MeHg and Pb, even at low doses, are toxic to iv rodents. Moreover, since niacin presented relevant antioxidant and antigenotoxic effects, supplementation with this vitamin can be an alternative to mitigate the toxic effects resulting from exposure to MeHg and/or Pb.

Made available in DSpace on 2017-07-10T17:37:17Z (GMT). No. of bitstreams: 1 Marcelo Goncalves dos Santos.pdf: 1187343 bytes, checksum: b267fd210df40a26f29e8e9d4e46f626 (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This study evaluated the remediation of soils contaminated with Cd and Pb with different dynamizations of homeopathic medicine Nux vomica and development of soybean and wheat grown in these soils. Therefore, we developed two experiments. The soils were contaminated with metals using CdCl2 and PbCl2H2O salts in three doses, based on the resolution of the research values (VI) of resolution No. 420 of CONAMA (dose 1 - value preexisting in the soil; dose 2 the VI and dose 3 - three times the VI) resulting in 0; 3 and 9 mg kg-1 for Cd, 89; 180 and 540 mg kg-1 for Pb. The dynamizations of homeopathic medicine Nux vomica utilized were 0, 12, 24, 48, 96, 200 and 400CH (centesimal hahnemanianna), being the witness (0CH) distilled water. The applications of the medicament in soil were days before and at sowing, while plants were applied in intervals of 14 days until complete the cycle. It was evaluated the development and gas exchange during the crop growing season. At flowering were evaluated the nutritional composition of plants determining the levels of N, P, K, Ca, Mg, Cu, Zn, Fe, Mn as well as Cd and Pb. At the end of the cycle the production of components were quantified. Subsequently, the plants were sectioned in plant organs and the bioavailability of the metals in their tissues. In soybean plants the dynamizations of homeopathic medicine Nux vomica changed height, stem diameter and gas exchange, and the soil contamination with Cd and Pb changed all variables. In wheat plants, homeopathic medicine interfered only in height and diameter of the stem being that contamination by Cd and Pb did not interfere with gas exchange, but negatively affected the development, mineral nutrition, roots system and plant productivity. It is concluded that the homeopathic medicine Nux vomica is effective for plant development of soybean and wheat grown in soil contaminated with Cd and Pb, however did not interfere in phytoavailability of metals to plants / O presente trabalho avaliou a remediação de solos contaminados com Cd e Pb com diferentes dinamizações do medicamento homeopático Nux vomica, e o desenvolvimento de plantas de soja e trigo cultivadas nestes solos. Para tanto, foram desenvolvidos dois experimentos um para cada cultura. Os solos foram contaminados com os metais utilizando os sais de CdCl2 e PbCl2H2O em três doses baseadas nos valores de investigação (VI) da resolução Nº 420 do CONAMA (dose 1 - valor preexistente no solo; dose 2 - o VI e dose 3 - três vezes o VI) resultando em 0; 3 e 9 mg kg-1 para Cd, 89; 180 e 540 mg kg-1 para Pb. As dinamizações do medicamento homeopático Nux vomica utilizadas foram 0, 12, 24, 48, 96, 200 e 400CH (centesimal hahnemanianna), sendo a testemunha (0CH) água destilada. As aplicações do medicamento no solo foram dias antes e na semeadura, enquanto que nas plantas as aplicações ocorreram em intervalos de 14 dias até terminar o ciclo das culturas. Foram avaliados o desenvolvimento e as trocas gasosas das culturas durante o período vegetativo. No florescimento foram avaliados a composição nutricional das plantas determinando os teores de N, P, K, Ca, Mg, Cu, Zn, Fe, Mn além de Cd e Pb. Ao final do ciclo foram quantificados os componentes de produção. Posteriormente, as plantas foram seccionadas em órgãos vegetais e determinadas a fitodisponibilidade dos metais nos respectivos tecidos. Nas plantas de soja as dinamizações do medicamento homeopático Nux vomica alteraram a altura e o diâmetro do caule bem como as trocas gasosas, sendo que a contaminação dos solos com Cd e Pb alterou todas as variáveis analisadas. Nas plantas de trigo, o medicamento homeopático interferiu na altura e diâmetro do colmo sendo que a contaminação por Cd e Pb não interferiu nas trocas gasosas, porém afetou negativamente o desenvolvimento, nutrição mineral, sistema radicular e produtividade das plantas. Conclui-se que o medicamento Nux vomica foi eficiente para o desenvolvimento de plantas de soja e trigo cultivados em solos contaminados com Cd e Pb, contudo não interferiu na fitodisponibilidade dos metais para as plantas

Objetivou-se neste trabalho avaliar a remoção e degradação de surfactante aniônico alquilbenzeno linear sulfonado (LAS) em esgoto sanitário do município de São Carlos – SP empregando o reator anaeróbio de leito granular expandido (EGSB - Expanded Granular Sludge Bed) em escala piloto, com TDH de 36 horas e temperatura mesofílica (±35ºC), instalado na ETE de São Carlos. Análises físico-químicas e cromatográficas foram realizadas para a caracterização do esgoto sanitário e monitoramento do reator EGSB. Foi observado no esgoto sanitário concentração de DQO bruta e LAS de 653,50 ± 169,30 mg L-1 e 6,189 ± 3,25 mg L-1, respectivamente. Em relação ao Ferro e metais potencialmente tóxicos, foram observados no esgoto sanitário os seguintes compostos: Cádmio, Chumbo, Ferro, Manganês, Níquel e Zinco. Em relação aos compostos recalcitrantes foram observados Butil Benzenosulfonamida, Ácido Hexadecanóico, Limoneno, Terpineno, Fenol, Álcool Feniletílico, Indolizina, Cafeína e Isobutil Octadecil Ftalato. O reator EGSB foi monitorado durante 314 dias e observou-se para DQO afluente e efluente, respectivamente, 265,82 ± 82,36 mg L-1 e 63,24 ± 40,67 mg L-1. Em relação ao LAS observou-se 7,35 ± 3,76 mg L-1 e 3,32 ± 3,08 mg L-1, respectivamente. Verificou-se 60,37 ± 29,84% de remoção de LAS. Observou-se durante toda operação pH próximo a neutralidade (7,26 ± 0,31), alcalinidade total efluente de 234,61 ± 64,39 mgCaCO3 L-1 e ácidos orgânicos voláteis efluente de 88,26 ± 23,68 mg L-1. Por meio do balanço de massa constatou-se que 56,2% do LAS foram removidos, compreendendo 12,8% por adsorção e 43,4% por biodegradação. Ao longo da operação do EGSB observou-se desestruturação e diminuição do tamanho médio dos grânulos, tal fato corrobora com a maior concentração efluente de sólidos totais e sólidos totais voláteis no primeiro mês e ao final da operação em comparação com a média geral de sólidos efluentes. Foram identificados por meio da plataforma Illumina MiSeq, 18 gêneros relacionados a degradação do LAS, tais como Synergistes, Syntrophorhabdus, Syntrophus, Clostridium, Geobacter e Desulfovibrio. / This study purpose was to evaluate the Anionic Surfactant Linear Alkylbenzene Sulfonate (LAS) in sanitary sewage from the city of São Carlos using an anaerobic expanded granular sludge bed reactor (EGSB), at pilot scale, with 36 hours TDH and (± 35ºC) mesophilic temperature, installed at São Carlos wastewater treatment station. Physical-chemical and chromatographic analyzes were performed for sanitary sewage characterization and EGSB reactor monitoring. It was observed an amount of 653,50 ± 169,30 mg L-1 in the raw sewage COD and an amount of 6,189 ± 3,25 mg L-1 in LAS. Regarding the potentially toxic metals, the following compounds were observed in the sanitary sewage: Cadmium, Lead, Iron, Manganese, Nickel and Zinc. Concerning recalcitrant compounds, Butyl Benzenesulfonamide, Hexadecanoic Acid, Limonene, Terpinene, Phenol, Phenylethyl Alcohol, Indolizine, Caffeine and Isobutyl Octadecyl Phthalate were observed. The EGSB reactor was monitored for 314 days and was observed for affluent and effluent COD, respectively, 265.82 ± 82.36 mg L-1 and 63.24 ± 40.67 mg L-1. In relation to LAS, were observed 7.35 ± 3.76 mg L-1 and 3.32 ± 3.08 mg L-1, respectively. There was 60.37 ± 29.84% LAS removal. It was observed, during the whole operation, pH close to neutrality (7.26 ± 0.31), total effluent alkalinity of 234.61 ± 64.39 mg.CaCO3.L-1 and volatile organic acids effluent of 88.26 ± 23, 68 mg L-1. By mass balance it was verified that 56,2% of the LAS were removed, comprising 12,8% by adsorption and 43,4% by biodegradation. During the EGSB operation, it was observed a disintegration and a decrease in the average granules size, fact that corroborates with higher total solids effluent concentration and total volatile solids in the first month and at the end of the operation compared to general effluent solids average. 18 genres related to LAS degradation were identified through the Illumina MiSeq platform, such as Synergistes, Syntrophorhabdus, Syntrophus, Clostridium, Geobacter and Desulfovibrio.