Um dos maiores problemas enfrentados pelas grandes cidades tem sido o gerenciamento de seus resíduos sólidos, principalmente no que tange seu descarte. Condições inadequadas de disposição desses resíduos causam inúmeros danos ao meio ambiente. Em cidades litorâneas é bastante comum a utilização dos manguezais como locais de disposição do lixo, resultando em sua degradação parcial ou mesmo total, levando muitas vezes ao desaparecimento desses ecossistemas. Durante mais de 50 anos a área de manguezal estudada neste trabalho serviu como local de descarte de resíduos provenientes das diversas atividades portuárias sendo utilizada como lixão e mesmo como aterro. Com o objetivo de estudar o comportamento geoquímico de íons de metais pesados chumbo, zinco, cobre e níquel foram analisados e estudados os atributos do solo/sedimento e as águas subterrâneas e superficiais do mar e do Rio Saboó, compartimentos próximos a área de estudos. Através de extrações parciais constatou-se que esses íons encontram-se acima dos valores de Referência de Qualidade da CETESB. O elevado teor de matéria orgânica, característico em área de manguezal, assim como a presença de minerais como illita, de elevado poder adsortivo, foram os principais responsáveis pela fixação iônica apesar das características texturais areno siltosa da área. A presença de íons de metais pesados nas águas subterrâneas e superficiais acima dos Padrões de Referência se deve ao contato do solo/sedimento com soluções com elevados valores de força iônica. Análises químicas do chorume, produto da percolação do antigo lixão, indicaram penas a presença de Pb em quantidades mais elevadas devido, principalmente, ao fenômeno de complexação com a matéria orgânica. / One of the biggest problems big cities are facing is how to manage its solid wastes, especially when we are talking about its disposal. Inadequate condition of its disposal causes many damages to environment. In coast cities are very common the use of mangroves as garbage disposal resulting in its partial or total degradation leading, many times, to ecosystems disappearances. For over 50 years the mangrove site studied in this project was the place of residual disposal from several harbor activities been used as landfill. With the aim to study the geochemistry behavior of ions of hevy metals, such as lead, zinc, copper and nickel, were analysed and studied the attributes of soil/sediment, groundwater and surface water from Saboó river, compartment close to the study field. Through partial extraction was proved that these ions were found above the values from Quality References of CETESB. High content of organic matter, characteristic in mangroves sites, just like the presence of minerals such as illite, which is very adsorptive, were the main responsible from ionic fixation despite the sandy-silty grains size characteristics of the area. The presence of ions in groundwater and superficial waters above the Reference Standarts is due to the contact of soil/sediment with solutions with high values of ionic force. Chemistry analysis of leachate, percolations product of the former landfill, indicated the presence only of Pb in high amount because of complexation phenomenon with the organic matter.

FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / As pesquisas com salinizaÃÃo nos perÃmetros irrigados, quanto à presenÃa de metais pesados ainda sÃo incipientes. Estes metais vÃm sendo encontrados em Ãreas irrigadas e estÃo associados a grupos de impactos ambientais, por serem poluentes devido à sua toxicidade e persistÃncia no ambiente. O trabalho teve como objetivo verificar a concentraÃÃo de metais pesados e verificar as correlaÃÃes existentes entre eles em solos afetados por sais referentes a quatro (4) perÃmetros irrigados no Cearà (Baixo-acaraÃ; Morada Nova; Curu-Pentecoste e IcÃ-Lima Campos). Foram coletadas amostras de solo nas profundidades de 0â10 e 10-20 cm em 10 pontos dentro de cada perÃmetro, sendo (1) ponto, dentro de cada perÃmetro, referente a solos de vegetaÃÃo preservada, totalizando oitenta (80) amostras. Foram obtidos os teores pseudototais de metais, assim como foram realizadas anÃlises multivariadas (anÃlise de correlaÃÃo canÃnica e fatorial), entre atributos relacionados com a salinizaÃÃo (CTC, PST, pH e CE) e variÃveis constituÃdas pelos metais pesados (Al, B, Mn, Mo, Si, Zr, Cr, Fe, V, Ni, Pb, Ti, Zn, As, Cd, Co e Cu) na camada de 0-10 e 10-20. Concluiu-se que: a) Os teores de metais pesados e elementos nos solos dos quatro perÃmetros seguiram a seguinte ordem decrescente: Fe, Al, Si, Ti, Mn, Zn, Cr, V, Ni, Cu, Co, B, Pb, Se, Cd, Mo, Zr, sendo esta ordem, no geral, independente das camadas superficiais e subsuperficiais consideradas. b) Os valores de referÃncia de qualidade para metais pesados e elementos obtidos neste estudo, de modo geral, foram considerados baixos, quando comparados com os valores estipulados por ÃrgÃos ambientais (CONAMA e CETESB). Inclusive, para todas as amostras de solo, os teores de As e Hg, ficaram abaixo de limite de detecÃÃo do aparelho (0,01). c) Os atributos do solo relacionadas com a salinizaÃÃo CTC, pH, PST e CE contribuÃram para explicar os teores de metais pesados nos solos dos quatro perÃmetros irrigados, quando analisados em conjunto; todavia, nÃo foram capazes de explicar quando analisados de forma individual; seguindo a ordem de importÃncia: CTC > pH > PST > CE. d) Foram verificadas correlaÃÃes entre os elementos metÃlicos analisados neste estudo (B, Mo, Si, Zr, Cr, Ni, Pb, Ti, Zn, Cd, Co, Se e Cu) com o Fe, Mn, Al, Ti e V, ou, ainda, afinidades geoquÃmicas entre os elementos, nos solos dos quatro perÃmetros irrigados do CearÃ. / Researches with salinization in irrigated areas, for the presence of heavy metals are still incipient. These metals have been consistently found in areas irrigated groups and are associated with environmental impact, being pollutants because of their toxicity and persistence in the environment. The study aimed to determine the concentration of heavy metals and to establish correlations between them in salt affected soils less than four (4) in irrigated Cearà (Baixo-AcaraÃ; Morada Nova; Curu-Pentecost and Ico-Lima Campos). Samples were collected at depth of 0-10 and 10-20 cm in 10 points within each perimeter, being (1) point within each perimeter, referring to soils preserved vegetation, totaling (80) samples. Were obtained the total contents of metals, as well as multivariate analyzes were performed (canonical correlation analysis and factorial) between attributes related to salinization (pH, CE, CTC and PST) and variable consisting of the heavy metals (Al, B, Mn , Mo, Si, Zr, Cr, Fe, V, Ni, Pb, Ti, Zn, As, Cd, Co and Cu) in the 0-20 cm. It was concluded that: a) The levels of heavy metals and elements in soils of the four perimeters followed the following order: Fe, Al, Si, Ti, Mn, Zn, Cr, V, Ni, Cu, Co, B, Pb , Se, Cd, Mo, Zr, and this order, in general, independent of the surface and subsurface layers considered. b) The reference values for heavy metals and quality data obtained in this study, in general, were low compared to the values stipulated by environmental agencies at Brasil (CONAMA and CETESB). In fact, for all the soil samples, the levels of As and Hg were below the limit of detection apparatus (0.01). c) Soil attributes related to salinity CTC, pH, EC and PST contributed to explain the levels of heavy metals in soils of the four irrigation schemes, when analyzed together, however, were not able to explain when analyzed individually. Following the order of importance: CTCT > pH > PST > EC. d) Correlations were observed between metallic elements analyzed in this study (B, Mo, Si, Zr, Cr, Ni, Pb, Ti, Zn, Cd, Co, Se and Cu) with Fe, Mn, Al, Ti and V, or even, geochemical affinities between the elements in the four soils irrigated CearÃ.

Na Região Metropolitana de São Paulo, em uma área impactada por resíduos de galvanoplastia estudaram-se fenômenos de fixação e mobilidade dos íons Ni, Cu e Cr associados ao solo e águas subterrâneas e superficiais. No solo, próximo à área de descarte do resíduo, detectou-se preocupante enriquecimento em íons metálicos na forma precipitada/adsorvida, disponíveis ao meio ambiente em função das condições ambientais. Baixos valores de CTC e matéria orgânica do solo constituído essencialmente por caulinita, bem como a declividade do terreno, favoreceram a mobilização iônica com fixação no terreno próximo ao Rio Aricanduva. Experimentalmente, através de lixiviações em extrator do tipo sohxlet e em colunas de percolação sob diferentes condições, demonstrou-se que o Ni é intensamente mobilizado, que o cromo praticamente mantem-se fixo e o cobre teve comportamento intermediário. Em trabalhos de campo verificou-se que o comportamento dos íons foi o mesmo, isto é, o cromo, na forma de óxi-hidróxido, se manteve precipitado junto às partículas do solo; o cobre, pouco ou quase nada se alterou, encontrado praticamente fixo (Cu(OH)2, CuO.nH2O) e o níquel apresentou comportamento dividido entre a solução intersticial e como íon adsorvido. Os resíduos galvânicos, embora sejam diferenciados quanto a composição química, em geral, mesmo em condições ambientais e características diversas dos solos, liberam elevadas concentrações de íons de metais pesados para o meio ambiente excedendo os limites estabelecidos pela CETESB. / In a contaminated site by electroplating wastes located in the Metropolitan region of São Paulo, São Paulo State, were studied phenomena of Ni, Cu and Cr ions fixation and mobility, associated with soils and superficial and groundwater water. The soil situated nearby an irregular area of waste disposal, presented high concentrations of heavy metals as adsorbed/precipitated ions, in available state depending on climate conditions. Low values of cationic exchange capacity (CEC), low organic matter content in soils and kaolinite dominant mineralogy, in addition to land slope favored ionic mobilization followed by its fixation in soils near Aricanduva River. Extractions with sohxlet extractor and with percolation columns in different conditions, show that the nickel is intensely mobilized and chromium remained precipitated; copper behavior was mediator. In works in study area the ions behavior was same, Cr as oxi-hydroxide, remained precipitated in soil; Cu is fixed (Cu(OH)2, CuO.nH2O) and Ni was distributed between soil and water. Solid waste produced by electroplating industry activities present high concentrations of heavy metals, regardless the different conditions and characteristics of soils, when inadequately dumped or disposed, heavy metals ions are released to environment, normally exceeding CETESB (environmental protection agency of São Paulo State) limits.

Orientador: Meuris Gurgel Carlos da Silva / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T12:46:26Z (GMT). No. of bitstreams: 1 AlmeidaNeto_AmbrosioFlorenciode_D.pdf: 8740127 bytes, checksum: 97f85966180df66452b1975b682bc9e1 (MD5) Previous issue date: 2011 / Resumo: A remoção de metais pesados por argilas, baseada na tecnologia de purificação da água, tem sido investigada como uma alternativa aos métodos tradicionais. Argilas do tipo esmectítico são as de maior utilização industrial, sendo considerada a mais interessante das argilas industriais. Todavia em diversos casos faz-se necessário submetê-las a tratamentos físicos e químicos para aprimorar suas potencialidades. Assim, estudou-se, no presente trabalho a remoção dos íons cobre e mercúrio, em laboratório a partir de soluções sintéticas, a adsorção sobre as argilas calcinadas dos tipos Bofe e Verde-lodo. Tais íons são recorrentemente produzidos e acumulados no meio ambiente e sua recuperação, para posterior reuso, tem cada vez mais importância a medida que não apenas o tratamento da água residuária e necessário, mas o aproveitamento dos subprodutos e incentivado, por acarretar benefícios econômicos e ambientais. Dessa forma, estudos a respeito de técnicas de remoção dos íons metálicos, assim como do equilíbrio e da cinética do processo, são necessários para a viabilização do procedimento de recuperação. As técnicas de remoção abordadas nesse trabalho foram a de banho finito e de leito fixo e seus objetivos foram avaliar os mecanismos e taxas de remoção dos íons de cobre e mercúrio, a partir do levantamento das curvas de equilíbrio e cinéticas de cada íon. Os ensaios monocomponentes, em banho e leito, mostraram que o cobre tem afinidade pelos sítios das argilas, mas o mercúrio não. As maiores capacidades de adsorção do cobre foram de 0,14 e de 0,22 mmol/g, em leito, sobre as argilas Bofe e Verde-lodo calcinadas, respectivamente. Quanto ao resultado de adsorção binária observa-se, que a remoção do mercúrio foi um pouco melhor, comparando com a remoção quando este metal encontrava-se em solução monocomponente. Provavelmente, devido ao efeito sinérgico, o cobre adsorvido favoreceu a remoção do mercúrio. A remoção do mercúrio na mistura binária foi reduzida quando o cobre apresentou porcentagens de remoção inferiores a 95%. Para regeneração dos leitos de argila calcinada foram utilizados diferentes eluentes. Estes ensaios foram realizados através de diversos ciclos de remoção/eluição utilizando colunas de leito fixo. Os resultados indicaram que a regeneração do leito com NaCl/HCl ou água salina a pH 3 e bastante eficiente, sendo a eluição de ate 100% e um crescimento na remoção foi observado após a exposição do leito ao eluente / Abstract: The water purification based on technology the metal removal by clays has been investigated as an alternative to traditional methods. Smectite clays have the major industrial use besides being considered the most interesting clays. However in many cases is necessary submitting them physical and chemical treatments with the aim of enhancing their capabilities. Thus, we studied in the present project the removal of copper and mercury of synthetic solutions in the laboratory moreover the adsorption on the calcined clays types Bofe and Verde-lodo. These ions are commonly produced and accumulated in the environment and their recovery for their reuse has become increasingly important not only for the treatment of wastewater in addition the utilization of the byproducts achieve economic and environmental benefits. Studies on techniques for removal of metal ions, as well as equilibrium and kinetics of the process are necessary for the viability of the recovery procedure. The removal techniques discussed in this study were realized in the finite bath and fixed-bed with the purpose to evaluate the mechanisms and removal ions rates of copper and mercury, the time of equilibrium and kinetic curves of each ion. Tests single component, in the bath and fixed-bed have showed that the copper has affinity with the clays, in contrast with the results obtained for the mercury. The highest adsorption capacities of copper were 0.14 and 0.22 mmol/g, in fixed-bed, on the Bofe and Verde-lodo calcined clays, respectively. The tests carried out in binary adsorption evidence that the removal of mercury was slightly better in comparison with removing this metal in a monolithic solution. Probably due to the synergistic effect, copper adsorbed favored the removal of mercury. Mercury recovery on the binary mixture decrease when copper ions presented removal percents less than 95%. Deferent's types of eluents were utilized for calcined clays bed regeneration. These tests were performed through several removal/elution cycles using fixed bed columns. These results indicated that the regeneration of the bed with NaCl/HCl or saline water at pH 3 is very efficient, the elution was of 100% and an increase in removal was observed after exposure of the bed to the eluent / Doutorado / Engenharia de Processos / Doutor em Engenharia Química

Orientador: Raquel Fernanda Gerlach / Tese (doutorado) - Universsidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-17T21:19:54Z (GMT). No. of bitstreams: 1 Guerra_CarolinadeSouza_D.pdf: 3176996 bytes, checksum: 6a6a858103b094d2da736d8fe61a1248 (MD5) Previous issue date: 2010 / Resumo: Objetivos: Os objetivos deste estudo são: a) comparar as concentrações de chumbo em diferentes camadas de esmalte e dentina pré e pós-natal de dentes decíduos, coletados em: 1 - Santo Amaro, BA, 2 - Cubatão, SP, 3 - Ribeirão Preto, SP e Mato Leitão, RS, b) analisar a distribuição espacial do chumbo por microfluorescência de raios X com radiação Síncrotron. Métodos: Uma microbiópsia no esmalte foi realizada in vitro na superfície do esmalte e cinco amostras sucessivas de esmalte superficial foram removidas. O chumbo foi medido por Espectrometria de massa com plasma indutivamente acoplado, e o fósforo foi medido colorimetricamente para determinarmos a profundidade de biópsia. Pedaços de dentina pré-natal e pós-natal foram dissolvidos em ácido nítrico. Cortes longitudinais de algumas amostras de dentes decíduos foram analisados por micro-XRF. As áreas anatômicas foram: esmalte superficial (SE), subsuperficial do esmalte (SSE), dentina primária (PD), e dentina secundária (SD). Resultados: A mediana da concentração de chumbo no esmalte superficial dos dentes coletados em Santo Amaro foi estatisticamente superior ao dos dentes coletados em Ribeirão Preto, Cubatão e Mato Leitão (p <0,0001 para as comparações). A concentração de chumbo no esmalte não diferiu quando os resultados de Ribeirão Preto e Mato Leitão, ou de Cubatão e Mato Leitão foram comparados. A mediana da concentração de chumbo encontrada na dentina pré-natal e pós-natal dos dentes coletados em Santo Amaro foram estatisticamente superiores aos encontrados nos dentes de Ribeirão Preto e Cubatão (p <0,0001). Nenhuma diferença foi encontrada quando os valores da dentina pré e pós-natal de Ribeirão Preto foram comparados com os de Cubatão. O coeficiente de correlação de Spearman para a concentração de chumbo na dentina versus concentração de chumbo no esmalte foi estatisticamente significante para Ribeirão Preto (dentina pré-natal versus esmalte r= 0,3, p = 0,003, r = 0,3, p = 0,0013 e dentina pós-natal versus esmalte r = 0,27, p = 0,06 , r = 0,21, p = 0,15), e Santo Amaro (dentina pré-natal versus esmalte r = 0,38, p = 0,0001, r = 0,18, p = 0 , 08 e dentina pós-natal versus esmalte r = 0,3, p = 0,015, r = 0,2, p = 0,1). Nenhuma correlação significativa foi encontrada em Cubatão (r dentina pré-natal = 0,118, p = 0,195, r = 0,05, p = 0,59, r = 0,05 dentina pós-natal, p = 0,59, r = 0,09, p = 0,28). A ?- SRXRF confirmou uma distribuição heterogênea de chumbo nos incisivos decíduos, com o maior sinal encontrado em esmalte superficial e dentina interna. A intensidade de Pb / Ca diminuiu da superfície do esmalte à dentina secundária em todas as amostras analisadas. Conclusões: este estudo mostra que existe uma correlação fraca, porém significativa entre os níveis de chumbo encontrado no esmalte superficial e na dentina pré e pósnatal, nas amostras provenientes de cidades que apresentaram maiores valores de chumbo (neste estudo Ribeirão Preto e Santo Amaro). A ?-SRXRF confirmou uma distribuição heterogênea de chumbo nos incisivos decíduos, com o maior sinal encontrado em esmalte superficial e dentina interna / Abstract: Objectives: The objectives of this study are: a) to compare the concentrations of lead in different layers of enamel with those found in prenatal and postnatal dentine of primary teeth collected from: 1 - Santo Amaro, Bahia State, 2 - Cubatão, São Paulo State, 3 - Ribeirão Preto, São Paulo State and Mato Leitão, Rio Grande do Sul State b) analyze the spatial distribution of lead in same samples by micro X-Ray Fluorescence with Synchrotron Radiation . Methods: A surface enamel acid-etch microbiopsy was performed in vitro in the enamel surface and five sucessives samples of superficial enamel were removed. Lead was measured by Inductively coupled plasma mass spectrometry, while phosphorus was measured colorimetrically to establish biopsy depth. Pieces of prenatal and postnatal dentine were dissolved in ultrapure nitric acid. Longitudinally cut of some samples of primary teeth were analyzed by micro-XRF. Four anatomical areas were analyzed by bidimensional (x, y) scanning in each tooth section. These anatomical areas were: Superficial enamel (SE), Subsuperficial enamel (SSE), Primary Dentine (PD), and Secondary Dentine (SD). Results: Median superficial enamel lead content of the teeth collected in Santo Amaro were statistically higher than the one from teeth collected in Ribeirão Preto, Cubatão and Mato Leitão (p<0.0001 for these comparisons). The lead concentration in the enamel did not differ when results from Ribeirão Preto and Mato Leitão, or Cubatão and Mato Leitão were compared. Median lead contents found in prenatal and postnatal dentine of Santo Amaro teeth were statistically higher than the ones found in teeth from Ribeirão Preto and Cubatao (p<0.001). No difference was found when prenatal and postnatal dentine values from Ribeirão Preto were compared with those from Cubatao. Spearman's correlation coefficient for lead concentration in dentine versus lead concentration in the enamel surface was significant for Ribeirão Preto (Prenatal dentine versus enamel r=0,3, p=0,003 e r=0,3, p=0,0013 and Posnatal dentine versus enamel r=0,27, p=0,06 e r=0,21 e p=0,15), and Santo Amaro (Prenatal dentine versus enamel r=0,38, p=0,0001 e r=0,18 e p=0,08 and Postnatal r=0,3, p=0,015 e r=0,2, p=0,1) . No correlation significant was found in Cubatão (Prenatal dentine r=0,118, p=0,195, r=0,05, p=0,59; Postnatal dentine r=0,05, p=0,59, r=0,09, p=0,28). The ?-SRXRF confirmed a heterogenous distribution of lead in the primary incisors, with the highest signal found in superficial enamel and inner dentine. The Pb/Ca intensity decreased from surface enamel to secondary dentin in all the samples analyzed. Conclusions: this study shows that there is a weak but significant correlation between the lead levels found in the superficial enamel and the ones found in the pre- and postnatal dentine, but only in the samples from cities that showed higher lead values (in this study Ribeirao Preto and Santo Amaro). The ?-SRXRF confirmed a heterogenous distribution of lead in the primary incisors, with the highest signal found in superficial enamel and inner dentine / Doutorado / Histologia e Embriologia / Doutor em Biologia Buco-Dental

Orientador: Osvaldir Pereira Taranto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenhariaa Quimica / Made available in DSpace on 2018-07-26T12:18:13Z (GMT). No. of bitstreams: 1 Silva_JeanFerreira_M.pdf: 3341187 bytes, checksum: 23040a974ec5a8dffb2801cb1dc12887 (MD5) Previous issue date: 2000 / Resumo: Os efluentes de muitos processos industriais possuem elevados teores de metais pesados, que em grande parte são lançados nos mananciais, levando à poluição dos recursos hídricos. Existem vários processos de tratamento destes efluentes, mas, em especial, um vem merecendo destaque: o processo de retenção destes metais por algas. As algas são usadas na recuperação ambiental promovendo a remoção de metais pesados, visando reaproveitar estes metais para fins industriais. O objetivo deste trabalho consiste em implementar programas computacionais em linguagem Fortran, juntamente com dados experimentais obtidos através da literatura para a modelagem de processos batelada e contínuo para retenção destes metais pela biossorção através de biomassas (algas). Este estudo foi feito para que o efluente contenha somente um metal pesado e assim não tenha interferência e competição de outros metais. Dados experimentais obtidos pela literatura conduzidos em banho finito, utilizados como parâmetros para o estudo do processo descontínuo, permitiram a quantificação de parâmetros de equilíbrio e de transferência de massa fluido-sólido. Após esta análise em processo descontínuo utilizou-se estes valores para uma primeira estimativa em um processo contínuo. Primeiramente foi feita uma modelagem em Batelada e assim conseguiu-se análise do coeficiente de transferência de massa e constantes de equilíbrio para o processo, análise das isotermas de Langmuir, Freundlich e por fim a modelagem em leito fixo. Resultados satisfatórios foram obtidos tanto para o processo descontínuo quanto para o contínuo em leito fixo com algas. Obtendo assim, curvas de equilíbrio, isotermas de adsorção, curvas de concentração para o processo batelada e curvas de concentração do tipo "breakthrough" na saída do leito para o processo contínuo / Abstract: Effluents of many industrial processes carry high levels of heavy metals, which in great part are disposed in the water sources, polluting them. There are many treatments for these effluents, but one, specially, is gainning importance: the retention of heavy metals using algae. Algae are used in environment recovery promoting retention of heavy metals, in order to reutilize them for industrial purposes. The objective of this work was to develop a computer program in Fortran and, along with experimental data from literature, model the batch and the continous process of heavy metals retention by biossorption. This study was carried out considering the effluent having only one kind of heavy metal, avoiding the influence or competition of other metaIs. Experimental data from batch processes taken ftom literature helped finding the equilibrium and the fluid-solid mass transfer parameters. After this analysis in batch process, these data were used to a first estimate of the continuous process. First, a batch modeling was done and it provided a good analysis of the mass transfer coefficient, the equilibrium constant, the Langmuir and the Freundlich isotherms and the fixed bed modeling. Satisfactory results were obtained to the batch process as much as for the continous algae fixed bed, providing equilibrium curves, adsorption isotherms, batch concentration curves and Breakthrough continous concentration curves / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Orientadores: Melissa Gurgel Adeodato Vieira, Ambrósio Florêncio de Almeida Neto / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T04:22:05Z (GMT). No. of bitstreams: 1 GaonaGalindo_LuzStella_M.pdf: 4431618 bytes, checksum: c30f71e68b49dd362a3ed8f70bde5a0a (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foi avaliada a capacidade de remoção de metais pesados comumente encontrados em efluentes e aterros sanitários da região metropolitana de Campinas, mais especificamente o chumbo e o cádmio, utilizando argila bentonítica sódica tipo Fluidgel extraída de jazias do nordeste brasileiro (Boa Vista - PB). A argila Fluidgel foi fornecida na forma comercial, composto de argila natural com a adição de carbonato de sódio. A argila Fluidgel comercial foi submetida a um tratamento ácido, uma vez que o pH natural desta ocasionava precipitação química do chumbo e do cádmio, sendo denominada Fluidgel TA. A argila Fluidgel comercial foi submetida ao tratamento térmico e químico por um período de 24 horas a temperatura de 750 ºC, com o objetivo de melhorar sua estabilidade física, sendo denominada Fluidgel TACal. As técnicas empregadas para a caracterização das argilas visando informações importantes para conhecer a viabilidade das suas propriedades na remoção de metais foram realizadas por termogravimetria (TG), calorimetria exploratória (DSC), difração de raios-X (DRX), espectroscopia de infravermelho (FTIR), área superficial, picnometria a gás hélio, microscopia eletrônica de varredura (MEV)/(EDS) e capacidade de troca catiônica (CTC). As técnicas de remoção estudadas neste trabalho foram a de banho finito e de leito fixo, permitindo avaliar os mecanismos e taxas de remoção dos íons de chumbo e cádmio, a partir da realização de curvas de equilíbrio e cinéticas de cada íon. A adsorção de Cd2+ e Pb2+ foi estudada em sistema estático e dinâmico para as argilas Fluidgel TA e Fluidgel TACal. A argila Fluidgel comercial não foi utilizada no processo de adsorção destes metais, já que seu alto teor de carbonatos ocasionou a precipitação química, além de não apresentar resistência mecânica adequada para aplicação posterior em sistema dinâmico de leito fixo. Os ensaios monocomponentes em sistema estático e dinâmico mostraram que o chumbo tem maior afinidade pelos sítios das argilas. Verificou-se a partir dos resultados obtidos em banho que as quantidades máximas adsorvidas pela argila Fluidgel TA foram de 0,038 e de 0,035 mmol de metal/g de argila, para o cádmio e o chumbo respectivamente. Utilizando argila Fluidgel TACal a quantidade máxima adsorvida de cádmio não foi significativa (0,005mmol/g), sendo para o chumbo de 0,033 mmol de metal/g de argila, podendo-se observar que a capacidade de remoção foi reduzida devido ao tratamento térmico. A partir das curvas de ruptura obtidas nas diferentes vazões verificou-se os diferentes comportamentos, indicando a forte influência da vazão nas resistências difusionais, mostrando que na vazão de 1 mL/min foi obtido um valor baixo de comprimento da ZTM (3,413), bem como uma baixa resistência à transferência de massa para a remoção de chumbo pela argila FluidgelTACal. Para regeneração dos leitos de argila FluidgelTACal foi utilizado o CaCl2 como eluente. A remoção do chumbo obtida até saturação do leito de argila FluidgelTACal, no primeiro ciclo foi de 0,03782 mmol/g, diminuindo no segundo e terceiro ciclos (0,02478 e 0,02060 mmol/g) / Abstract: This study aimed to evaluate the ability to remove heavy metals commonly found in industrial wastewater and landfills in the metropolitan region of Campinas, specifically lead and cadmium using as adsorbent sodic bentonite clay type Fluidgel, which was obtained from Boa Vista, Paraíba, located in the northeastem region of Brazil. Fluidgel was provided as a commercial product processed, being composed of natural clay with sodium carbonate addition. Fluidgel in nature was subjected to acid treatment because the pH of this clay occasioned chemical precipitation of lead and cadmium, it was named Fluidgel TA. In order to improve the physical stability, the Fluidgel clay was also carried out a chemical and thermal treatment for a period of 24 hours at 750 oC and it was named as Fluidgel TACal. The techniques employed for the characterization of clays seeking important information to identify the viability of their properties in the removal of metals and it was performed by thermogravimetry, scanning calorimetry, X-ray diffraction (XRD), Fourier transform infrared (FTIR), Thermal Analysis (TG and DSC), Scanning Electron Microscopy (SEM) with chemical analysis by Energy Dispersive X-ray (EDX), surface area, helium pycnometry, and cation exchange capacity. The removal techniques discussed in this work were realized in the finite bath and fixed bed with the purpose to evaluate the mechanisms and removal rates of lead and cadmium. The adsorption of Cd2+ and Pb2+ was studied in the finite bath and fixed bed systems using Fluidgel TA and Fluidgel TACal. Fluidgel was not used in the process of adsorption of these metals, due to their high content of carbonates caused the precipitation chemistry, besides it type of clay did not has mechanical strength suitable for application in dynamic system of fixed bed. According to obtained results, sorption affinity of clays towards lead is larger than their affinity towards cadmium. The results obtained in a finite bath showed that the maximum amount adsorbed by the clay Fluidgel TA was 0.038 and 0.035 mmol of metal/g of clay, for cadmium and lead, respectively. Using clay Fluidgel TACal the maximum amount of adsorbed cadmium was not significant (0.005 mmol / g), whereas for lead was of 0.033 mmol of metal / g of clay, can be observed that the removal capacity has been reduced due to heat treatment. Fixed bed experiments were developed evaluating the breakthrough curves obtained by different flow rates showed different behavior, indicating a strong influence on the flow rate of diffusional resistance, can observed that using the flow rate of 1 mL/min was obtained a low value of the length of the mass transfer zone (MTZ) of 3.413 and moreover, a low resistance to mass transfer to remove lead with Fluidgel TACal clay. The CaCl2 was used as eluent with the purpose to regeneration of the beds using Fluidgel TACal clay. The study conducted in fixed bed system for lead in cycles of adsorption/desorption showed that in the first cycle was 0.03782 mmol/g, reducing the second and third cycles (0.02478 and 0.02060 mmol /g) / Mestrado / Processos em Tecnologia Química / Mestra em Engenharia Química

Ph.D. / This study consisted of a two-tiered approach to assessment of the effects of EDCs on aquatic organisms, and heavy metal accumulation in the aquatic environment, by integrating field work and laboratory-based experiments. In the last three decades a considerable portion of research in aquatic health and aquatic toxicology has been largely focused on endocrine disruptors, aiming to establish how certain chemicals discharged into the environment, especially organochlorine pesticides (OCs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), surfactants and plasticisers, can mimic endogenous hormones and thereby induce reproductive abnormalities. The rationale behind the present study was the growing interest in the study of endocrine disrupting chemicals (EDCs) internationally and the aspects of this field of research that are relevant to South Africa’s aquatic environment and its endemic aquatic organisms. The field work was carried out in the Rietvlei Wetland System and consisted of a combination of plant root analysis and application of the South African Scoring System 5 (SASS5) macroinvertebrate index. Three characteristic wetland macrophytes used in the study were Typha capensis, Phragmites australis and Persicaria lapathifolia. Samples of plants, sediment and water were taken from predetermined locations along the wetland system in the Rietvlei Nature Reserve and analyzed for heavy metals by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The heavy metals analyzed in this study; lead, arsenic and cadmium, have also been implicated as endocrine disruptors. The results of heavy metal accumulation in the plant roots reflected a pollution trend along the wetland, suggesting that plant roots are useful bioindicators of contamination in freshwater systems.

There are many types of chemicals/contaminants present in the environment, ranging from synthetic chemicals to trace metals that are required for life. When an organism is exposed to a toxicant, adverse effects are generally first at the sub-organismal level. There is thus a need for physiological and biochemical indicators of organismal health and sub-lethal toxicant effects. A bio-indicator, or biomarker, is a response of a living organism to environmental changes or because of exposure to contaminants. The main objectives of this study were to evaluate and investigate the possible use of biomarkers as indicators of sub-lethal (chronic) effects induced by certain chemicals/pollutants on the Mozambique tilapia, Oreochromis mossambicus. The biomarkers were evaluated as a possible sensitive and reliable measure of effects due to exposure to pollutants. This study was divided into laboratory experiments and field evaluations. The laboratory experiments consisted of the evaluation of biomarkers in exposure studies on 18-24 day old O. mossambicus juvenile fish, to determine the sub-lethal effects induced by chemicals. Acetylcholinestrase (AChE), Ethoxyresorufin-O-deethylase (EROD) and glucose levels acted as the battery of biomarkers evaluated. Thirty (30) juvenile fish were exposed for 24 and 96-hours to sub-lethal concentrations of cadmium, zinc, pentachlorophenol (PCP) and cyanide. For the field evaluation, mature Oreochromis mossambicus of both sexes, were caught during the summer and winter at the Rust de Winter Dam, Loskop Dam and Hartebeespoort Dam. Rust de Winter Dam acted as the reference site. The biomarkers evaluated during the field studies include: erythrocyte AChE, ƒx-Aminolevulinic acid dehydratase (ALAD) and plasma glucose levels, EROD and liver glycogen. The laboratory (exposure) test used during this study was not sensitive enough to obtain reliable, repeatable results. But standardised procedures were established for possible use in future studies. During the field studies, ALAD, EROD and plasma glucose showed significant results and differences between the reference and polluted sites. More accurate results could be obtained at impoundments with higher levels of pollution. Although, erythrocyte AChE and liver glycogen did not show significant results during this study, they might also show more accurate and reliable results at higher levels of pollution. In future, chemical water analysis should be carried out during field evaluation to determine what chemicals/toxicants are present in the aquatic environment. Biomarkers will show the level of effects of the toxicant on the organism, while chemical analysis will determine the specific pollutant present in the water. / Prof. J.H.J. Van Vuren

Growing interest in biofuel production from non-fossil fuel sources has resulted in several studies exploring different raw material sources as feedstock, including many algae species, for large-scale production of biofuel. Algae are promising feedstock due to advantages such as its short growth cycle, high biomass production, and lipid content. However, there are still challenges to overcome in order to use algae for commercial biofuel production. One of these challenges is the requirement for a large quantity of water and nutrients needed for growing large quantities of the algae. This work explores a potential solution to this challenge by studying the possibility of using industrial wastewater to grow algae for biofuel production. However, many industrial wastewaters, including effluents from semiconductor processing plants, are known to contain heavy metals that are toxic to humans and the environment. In this work, the effects of four of such metals ions, As(V), As(III), Ga(III), and In(III) on Chlorella sorokiniana and Scenedesmus obliquus strains were studied. In particular, the heavy metal toxicity on the strains, effects on its growth rate, biomass yield, lipid content and fatty acid methyl esters (FAME) were studied. Also, the effect of controlling pH on growth rate, biomass yield, lipid content, and FAME was studied for Chlorella sorokiniana in the presence of Ga(III). The results of the study confirmed the toxicity of these metals on both strains. However, Ga(III) and In(III) had the highest effect, while As(V) showed the least toxicity to the strains, with Chlorella sorokiniana withstanding concentrations of As(V) as high as 140mg/L. The heavy metals were slightly more toxic to Scenedesmus obliquus compared to Chlorella sorokiniana. In addition, the heavy metals reduced the growth rate of both strains. High percent changes in growth rate (more than 50%) were seen in cultures containing Ga(III) and In(III). Furthermore, concentration measurements with Inductively Coupled Plasma Optical Emission Spectrometer (ICP) before, during, and at the end of the growth period, showed that Scenedesmus obliquus adsorbed higher amounts of the heavy metals compared to Chlorella sorokiniana. Microalgae biosorption of heavy metals limits its end use, hence making Scenedesmus obliquus a less favorable option for this study, but may be a better choice for wastewater treatment applications. The effects of the four metals on the lipid content and FAME profile of Chlorella sorokiniana were studied. The result showed an increase in Chlorella sorokiniana lipid content in the presence of In(III), but a decrease in the presence of As(V) and As(III). The heavy metals had effects on the strain’s FAME compositions. The fatty acid composition included C16:0, C16:1, C16:2, C16:3, C18:0, C18:1, ω-6, C18:2, ω-6, and C18:3, ω-3 accounting for more than 97% of the total FAME composition. Furthermore, controlling the pH of the culture in the presence of Ga(III) at 6.5 led to higher adsorption of the heavy metal, increase in lipid content, but no significant change in FAME composition.