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.

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.

Magister Scientiae (Medical Bioscience) - MSc(MBS) / The South African economy relies heavily on mining. The residues of these activities contain harmful metals that are discharged into the environment as industrial wastes, contaminating the air, soil, surface and ground water. A lot of people who live in remote areas in South Africa rely on ground water to drink and cook. They also cultivate their own vegetables increasing the risk of metal toxicity. Some of these metals are very toxic and can cause adverse effects upon being ingested. Toxic metals are well known to be harmful to humans. Some of these metals are carcinogenic or nephrotoxic when a large amount is accumulated in the human body causing cancer and destroying tissues such as the kidneys. The detrimental health effects of these metals may take months to years before manifestation causing people to sideline them as hazards. One of the major toxic elements that are discharged into the environment is lead. A natural zeolite called clinoptilolite has been widely used as an adsorbent for toxic metals from contaminated water and from the human body because of its properties such as ion-exchange capacity and pore size. However, this natural zeolite clinoptilolite is not pure and may contain traces of toxic elements of which the nature and concentration depend on the origin of clinoptilolite. The structural stability of clinoptilolite in acidic or alkaline media is not well documented. The lack of documented information about the leachates of clinoptilolite and their long term effects on the human body may cause harm to people who ingest this zeolite. This has led to investigation of synthetic zeolites such as faujasite which has already been used for decontamination of sludge, industrial effluents and other waste water by removing toxic metals such as Pb, Cd, Cu, Zn and As. This study focuses on comparing the toxic metal removal efficiency of natural zeolite clinoptilolite (C), clinoptilolite-based faujasite (FAU3) and clinoptilolite-based ultrastable Y zeolite (USY3), from contaminated water and simulated gastric juice containing lead and cadmium and to evaluate the extent of leaching of other elements from these zeolites. Clinoptilolite was used as a starting material for the synthesis of faujasite (FAU3) which was further treated with oxalic acid to get an ultrastable Y zeolite (USY3). Various techniques were used to characterise the as-received clinoptilolite, faujasite zeolite and USY, namely XRD, SEMEDS, FTIR, solid state NMR (27Al and 29Si) and BET-N2. These characterisation techniques confirmed that clinoptilolite was successfully transformed into faujasite and that the treatment of faujasite with oxalic acid yielded USY3. A comparative adsorption study was conducted using three zeolite samples: namely Clinoptilolite (C), clinoptilolite-based faujasite (FAU3) and ultrastable Y zeolite (USY3). ICP was used to characterise the liquid samples and it was concluded that zeolites were efficient in removing lead and cadmium from contaminated water samples as well as from simulated gastric juice. Some leachates from these zeolites were also observed. A contaminated water sample containing lead and cadmium was used as a medium where the removal capacity and percentage removal with C, FAU3 and USY3 was investigated. It was observed that the optimum dosage varied from one zeolite to the other and also from one metal to the other. The optimum dosage for C, FAU3 and USY3 for the uptake of lead was found to be 0.2 g, 0.2 g and 0.05 g respectively while for cadmium it was 0.4 g, 005 g and 0.1 g, respectively. It was also shown in this study that the removal capacity for lead and cadmium could be hindered by the Na content in FAU3 and USY3 due to the fact that these metals could be in an uptake competition with Na and other cations that leached out or exchanged from the zeolites. It was observed that the optimum metal concentration for lead uptake as well as for cadmium with few metals being released back into the solution was 0.1 mg/L. The optimum contact time for both lead and cadmium was 15 minutes. The factor that varied depending on the type of metal was pH, which was at its optimum at 3.5 for lead and at 5.5 for cadmium. A simulated gastric juice was contaminated with toxic metals (lead and cadmium) and the zeolites were used to treat the contaminated samples. It was shown that the removal capacity of these zeolites increased with the increase in initial concentration of the metal. Time proved to be one factor that affected the behaviour of zeolites. The modification of the synthesised faujasite into an ultrastable Y zeolite proved to have played a role in increasing the removal of toxic metals and in preventing the high leaching of some elements out of the zeolite. / 2018-12-14

Submitted by Francisco Carlos Da Silva (fracarlos@hotmail.com) on 2018-10-22T16:30:22Z No. of bitstreams: 1 Tese -Repositorio final.pdf: 26926264 bytes, checksum: 56e13a425183936436178060a6f5c834 (MD5) / Approved for entry into archive by Lucimara Kurokawa Shinoda null (lucimaraks@sorocaba.unesp.br) on 2018-10-23T17:48:36Z (GMT) No. of bitstreams: 1 silva_fc_dr_soro.pdf: 26926264 bytes, checksum: 56e13a425183936436178060a6f5c834 (MD5) / Made available in DSpace on 2018-10-23T17:48:36Z (GMT). No. of bitstreams: 1 silva_fc_dr_soro.pdf: 26926264 bytes, checksum: 56e13a425183936436178060a6f5c834 (MD5) Previous issue date: 2018-08-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Os metais potencialmente tóxicos se acumulam frequentemente na zona não saturada do solo e quando em concentrações elevadas podem afetar tanto a biota quanto o aquífero freático. Neste trabalho foram avaliadas as concentrações de metais potencialmente tóxicos no solo do setor mais antigo da necrópole Nossa Senhora Aparecida na cidade de Piedade, SP. O estudo foi desenvolvido durante o período de 2015 a 2018. Inicialmente, foram realizados ensaios geofísicos utilizando as técnicas de Eletrorresistividade (equipamentos Syscal e Ohmmapper) e Eletromagnética Indutiva, com o objetivo de se localizar e dimensionar potenciais sítios anômalos. Após a interpretação dos resultados geofísicos, foram realizadas sondagens para coletas de amostras de solo nos sítios indicados por estas técnicas. As sondagens foram limitadas a três metros de profundidade com amostras coletadas a cada 0,5 m. Nas amostras foram quantificados por espectrometria de emissão óptica com plasma indutivamente acoplado ICP-OES os metais: bário, cádmio, chumbo, cobalto, cromo, cobre, manganês, molibdênio, níquel e zinco. Foram efetuados também os ensaios físicos do solo: granulometria, textura e permeabilidade com carga constante, estes visando compreender o comportamento e mobilidade dos metais. Os resultados das análises químicas indicaram um aumento na concentração, em relação a área de controle (background local) e em algumas profundidades esses aumentos ultrapassam os valores de referência e prevenção estabelecidos pela CETESB/16, dos metais Pb, Co, Cr , Co, Ni, Ba e Zn. O elemento Mo apresentou valores abaixo das orientações da CETESB/2016 mas com valores elevados em relação a área de controle e o Mn, apesar de estar muito elevado se comparado ao controle, não existe até o presente, valores de referência e prevenção estabelecidos pela CETESB/2016. A análise textural e granulométrica indicaram um solo não muito propício para sepultamentos (k = 10-4) segundo as normas brasileiras, mas, para uma avaliação mais criteriosa, devemos considerar as condições geoambientais locais (geomorfologia, pedologia, clima, ciclo hidrológico) e a profundidade do aquífero freático. / Potentially toxic metals are often accumulate in the unsaturated zone of the soil and when they are found in a high concentration can affect biota as much as the water's system/ Aquifer. In this work it was evaluated the potentially toxic metals concentration in the soil of the oldest sector of the necropolis Nossa Senhora Aparecida at the city Piedade, SP. The study was developed between 2015 and 2018. At first geophysical tests were done using the techniques of Elecal Resistivity, Ohmmapper Eletrorescence and Inductive Electromagnetic with the objective of locating and dimensioning potential anomalous sites. After an interpretation of the geophysical results soundings were done to collect samples of soil techniques in the areas indicated by this technique. The sounding were limited to three meters deep with samples collected every 0.5 m. The samples were quantified by ICP-OES inductively coupled plasma optical emission spectrometry: barium, cadmium, lead, cobalt, chromium, copper, manganese, molybdenum, nickel and zinc. Also were carried out Soil physical tests: granulometry, texture and permeability with constant load, aiming to understand the behavior and mobility of the metals. The results of the chemical analyzes indicate an increase of the concentration, in relation to the control area (local background) and in some depths these increases exceed the reference and prevention values established by CETESB / 16, metals Pb, Co, Cr, Co, Ni, Ba and Zn. The Mo element presented values below the CETESB / 2016 guidelines but with high values in relation to the control area and the Mn, although it is very high when compared to the control there are no reference and prevention values established by CETESB / 2016. The textural and granulometric analysis indicated a soil not very suitable for burials (k = 10-4) according to the Brazilian standards, but for a more careful evaluation we should consider local geoenvironmental conditions (geomorphology, pedology, climate, hydrological cycle) and the depth of the water table. / CAPES: 001

Submitted by Valquíria Barbieri (kikibarbi@hotmail.com) on 2018-04-06T20:16:40Z No. of bitstreams: 1 DISS_2014_Paulo Eduardo Reinach da Silva Gonçalves.pdf: 3069959 bytes, checksum: 7c8ac2afa091cf84c470aa2114a36f3f (MD5) / Approved for entry into archive by Jordan (jordanbiblio@gmail.com) on 2018-04-23T18:32:55Z (GMT) No. of bitstreams: 1 DISS_2014_Paulo Eduardo Reinach da Silva Gonçalves.pdf: 3069959 bytes, checksum: 7c8ac2afa091cf84c470aa2114a36f3f (MD5) / Made available in DSpace on 2018-04-23T18:32:55Z (GMT). No. of bitstreams: 1 DISS_2014_Paulo Eduardo Reinach da Silva Gonçalves.pdf: 3069959 bytes, checksum: 7c8ac2afa091cf84c470aa2114a36f3f (MD5) Previous issue date: 2014-03-28 / CAPES / A contaminação dos recursos hídricos está diretamente ligada às atividades antrópicas. Algumas dessas atividades estão relacionadas à presença de metais que uma vez na água causam grande preocupação, pois estes não possuem caráter de biodegradabilidade, podendo acumular na biota aquática e chegar a níveis elevados causando efeitos adversos para o ambiente e a saúde humana. As bacias do rio Cuiabá e São Lourenço são de grande importância, pois a água dos seus rios é utilizada para diversos usos, além de abrangerem as principais cidades de Mato Grosso e por serem afluentes do rio Paraguai, o principal rio formador do Pantanal. Frente ao exposto, o objetivo deste trabalho foi a determinação da concentração de Cu, Cr, Cd, Mn, Fe, Pb e Zn em águas superficiais e sedimentos de fundo de rio das bacias do Rio Cuiabá e São Lourenço, Mato Grosso, Brasil. Os metais nas amostras de água foram determinados por espectrometria de absorção Atômica em chama e por espectrometria de emissão atômica com plasma indutivamente acoplado e, as amostras de sedimento por espectroscopia de absorção atômica em chama. Os resultados obtidos foram comparados com os valores máximos permitidos (VMP) pela Resolução no 357/2005 para a água doce de Classe II e pela Canadian Council of Ministers of the Environment (CCME) para os sedimentos. A análise de agrupamento hierárquica (AHA) revelou a existência de quatro agrupamentos para as amostras de água e dois agrupamentos para as amostras de sedimento. Com intuito de avaliar a qualidade dos agrupamentos foi realizada uma análise discriminante (AD) que mostrou uma classificação correta em 80% para as amostras de água e 79% para as amostras de sedimento. Além disso, a AD no modo “stepwise forward” mostrou que foi possível reduzir o número de variáveis avaliadas mantendo a mesma eficácia na classificação dos grupos. Gráficos de excedência mostraram que a maior parte dos resultados de concentração dos metais encontrados ficou abaixo do limite estabelecido pela legislação. Porém atenção deve ser dada para Pb e Cr que tanto nas amostras de água, quanto nas de sedimento foram encontrados valores de concentração acima do estabelecido pela legislação em alguns pontos da bacia do rio Cuiabá e São Lourenço, possivelmente proveniente de atividades antrópicas, como descartes de efluentes domésticos e industriais. / Contamination of water resources is directly linked to anthropic activities. Some of these activities can release metals in the environment which, once in the water, cause great concern since they are not biodegradable, can accumulate in the biota and so reach critical levels causing adverse effects to human health and to the environment. The watersheds of Cuiabá and São Lourenço rivers are of great importance since their water is applied to multiple uses, involving the main municipalities of Mato Grosso State. Moreover they are the main affluent of Paraguay river which is the most important contributor to the Pantanal of Mato Grosso. Thus, this study aimed to determine the concentration of Cu, Cr, Cd, Mn, Fe, Pb and Zn in surface water and riverbed sediment of Cuiabá and São Lourenço watersheds. Metals were analysed in water using flame atomic absorption spectrometry and inductive couple plasma emission spectrometry and in sediment using flame atomic absorption spectrometry. The metal concentrations in water were compared to the maximum allowed values established in the Resolution CONAMA n. 357/2005 for class II river waters while for sediments the values established by the Canadian Council of Ministers of the Environment (CCME) were used for comparison. The hierarchical cluster analysis revealed the existence of four groups regarding water quality and two groups of sediment. Discriminant analysis (DA) was applied to evaluate the grouping quality showing a correct classification of 80% of water and 79% of sediment samples. A análise de agrupamento hierárquica (AHA) revelou a existência de quatro agrupamentos para as amostras de água e dois agrupamentos para as amostras de sedimento. Moreover, DA in stepwise forward mode showed that it was possible to reduce the number of evaluated variables keeping the same efficiency in the groups classification. Exceedence curves showed that the majority of metal concentrations were below the limits established in the legislation. However, especial attention should be given to Pb and Cr that were detected in concentrations above these limits in water as well as in sediment samples in some sampling points, probably related to anthropic activities such as domestic and industrial effluents discharge.