Durante o estudo de um sistema de tratamento de efluentes de uma indústria química, contendo em suas águas residuárias vários metais pesados foi observada a ineficiência no processo de nitrificação do efluente tratado. Diante dessa constatação, desenvolveu-se este trabalho visando estudar as interferências dos metais pesados, Pb2+, Zn2+ e Cu2+ no desempenho do processo de nitrificação em um sistema similar de tratamento. Para observação dos efeitos dos metais Zn2+, Pb2+ e Cu2+ isoladamente, foram montados 3 reatores e simuladas as concentrações afluentes do tanque de aeração da indústria. Outros três reatores alimentados com soluções contendo Zn+Cu, Zn+Pb e Pb+Cu utilizados para observação de possíveis efeitos de sinergismo e antagonismo. Um outro reator foi alimentado com a solução dos três metais (Zn2+, Cu2+ e Pb2+). Todos os reatores, recebendo adição de metal ou não, apresentaram concentrações muito elevadas de nitrito. Na realização do ensaio de NMP ficou evidente a inibição dos organismos oxidantes de nitrito, que pode ter ocorrido pela alta concentração do próprio nitrito, ácido nitroso ou amônia livre. Efeitos dos metais Zn2+ e Cu2+ não foram evidentes, o Pb2+ foi o único metal que apresentou efeito de inibição no processo de nitrificação. Os reatores que receberam combinação de íons metálicos não evidenciaram efeitos de sinergismo nem antagonismo, sendo que o reator que recebeu adição dos três íons apresentou menor eficiência. / During the study of the chemical industry effluent treatment system containing, several heavy metals, was observed an inefficiency in the nitrification process in final effluent. Therefore, this work was deve!oped to find out ofthe study of the interference of the heavy metals, Pb2+, Zn2+ and Cu2+ on the performance of nitrification process in a similar system of treatment. For observation of the effects of metals Zn2+, Pb2+ and Cu2+ separately, were established three reactors and simulate the influent concentration in the aeration tank of the industry. Other three reactors were fed with solution containing Zn+Cu, Zn+Pb and Pb+Cu for observation of possible synergism or antagonism effects. The other reactor was fed with a solution of the three metals (Zn2+, Cu2+ and Pb2+). All the reactors, receiving the addition of metaIs or not, presented very high concentrations of nitrite. In the realization of the test of NMP, the inhibition of the nitrite oxidizers organisms was evident, that might have happened due to high concentration of nitrous acid, free ammonia and nitrite. The effects of the metals Zn2+ and Cu2+ were not evident; but the Pb2+ was the only metal that presented inhibition effect in the nitrification process. The reactors that received the metallic ion combination didn\'t evidence neither synergism nor antagonism effects, however the reactor that received the addition of the three ions presented smaller efficiency.

A produção de lodo de esgoto vem aumentando exponencialmente com a multiplicação das estações de tratamento de esgoto (ETEs) e a sua disposição final tem se tornado um problema sanitário preocupante. Por ser um resíduo rico em matéria orgânica e nutrientes, muitas pesquisas vêm sendo desenvolvidas na busca de alternativas ecologicamente mais adequadas para o seu descarte. Este trabalho teve como objetivo verificar as diferenças entre lodos de esgoto (biossólidos), produzidos em três diferentes Estações de Tratamento de Esgotos da região metropolitana de São Paulo, quando utilizados como adubo em plantações de Eucalyptus grandis. Procurou-se também avaliar a influência deste resíduo sobre a ciclagem de nutrientes e sobre a dinâmica de metais pesados no ecossistema florestal. O estudo foi realizado na Estação Experimental de Ciências Florestais da ESALQ/USP em Itatinga-SP, cujo solo é predominantemente arenoso e de baixa fertilidade natural. O delineamento experimental utilizado foi em blocos aleatorizados, com 4 repetições e cinco tratamentos, sendo eles: 1)Testemunha Absoluta (TA), sem nenhuma adubação; 2) Fertilização mineral convencional (FM); 3) Aplicação de 15 Mg ha-1 de lodo de esgoto da ETE de Barueri (LB); 4) 15 Mg ha-1 de lodo de esgoto da ETE de São Miguel (LSM); 5) 15 Mg ha-1 de lodo de esgoto da ETE do Parque Novo Mundo (LPNM). Todos os tratamentos com lodo de esgoto foram complementados com potássio mineral (KCl), visto que o lodo é deficiente neste nutriente. O LB e o LSM foram condicionados com polieletrólitos, mas o LPNM foi condicionado com cal hidratada e cloreto férrico. O efeito dos diferentes tratamentos sobre os eucaliptos foi avaliado através de: inventários florestais semestrais, nutrição foliar, estimativa do folhedo produzido mensalmente, estimativa semestral de folhedo acumulado sobre o solo, avaliação da decomposição do folhedo no campo através de bolsas decompositoras, reflexo dos lodos sobre a fertilidade do solo, estimativa da biomassa e do estoque de nutrientes e metais pesados nos componentes do tronco (Lenho+Casca), nas folhas e nas raízes finas dos eucaliptos. Observou-se que a adubação dos eucaliptos com os lodos propiciou, em média, um incremento do volume de madeira da ordem de 65%, superior à testemunha (sem adubação) e similar ao observado no tratamento com fertilização mineral. A concentração dos nutrientes nas folhas dos eucaliptos tratados com os lodos, aos 6 meses de idade, apresentou uma elevação significativa dos nutrientes N, P, Ca, Cu, Fe e Zn em relação à testemunha. Mas, aos 42 meses, observou-se a tendência geral de redução da concentração de todos os nutrientes nas folhas, independente dos tratamentos. A adição dos lodos estimulou em 75% a produção de folhedo pelos eucaliptos, bem como um maior acúmulo de folhedo sobre o piso florestal. Conseqüentemente, houve uma maior transferência de nutrientes, via folhedo, das copas dos eucaliptos para a camada de serapilheira. De maneira geral, a aplicação da FM e dos lodos de esgoto melhorou a fertilidade do solo na linha de plantio (ponto de aplicação), principalmente na camada entre 0 e 5 cm de profundidade. Todavia, poucas mudanças foram observadas na produção de raízes finas em função dos diferentes tratamentos. O lodo de esgoto, quando condicionado na ETE com cal hidratada, tende a elevar o estoque de cálcio em todos os componentes do sistema solo-planta-serapilheira, podendo a longo prazo causar desbalanço nutricional e impactos prejudiciais ao ecossistema. Nos tratamentos com lodo de esgoto, foi observada uma maior concentração de metais pesados, em comparação à testemunha, nas folhas: Cu, Zn e Ni; no folhedo: Cu e Zn; no solo: Cu e Zn (na linha de plantio) e Zn (na entrelinha de plantio), apenas na camada de 0-5 cm de profundidade e nas raízes finas: Zn e Ni. É imprescindível, portanto, se conhecer previamente a concentração dos diferentes elementos no lodo de esgoto, antes de sua aplicação em plantios florestais. O monitoramento nutricional das árvores e da ciclagem dos nutrientes são práticas de fundamental importância para o bom manejo deste resíduo e do empreendimento florestal. / The production of sewage sludge increased exponentially with the enlargement of sewage treatment plants (ETEs, by its acronym in Portuguese). The final disposal of this product has always been a sanitary problem. Since it is a residue rich in organic matter and nutrients, several researches have been carried out, looking for adequate ecological alternatives for its disposal. This study aims to verify the differences among the sewage sludge (biosolids) from three different sewage treatment plants in the metropolitan region of Sao Paulo when used as fertilizers in Eucalyptus grandis plantations. Moreover it seeks to assess the influence of this residue in the nutrients cycling and in the heavy metals dynamic in forestry ecosystems. This research was carried out in the Experimental Station of Forestry Sciences of ESALQ/USP in Itatinga, Sao Paulo, where the soil is mainly sandy and of low natural fertility. The experimental delineation was of randomized blocks, with 4 replications and 5 treatments: 1) control (TA) without fertilization; 2) mineral conventional fertilization (FM); 3) application of 15 Mg ha-1 of sewage sludge from Barueri ETE (LB); 4) 15 Mg ha-1 of sewage sludge from Sao Miguel ETE (LSM); 5) 15 Mg ha-1 of sewage sludge from Parque Novo Mundo ETE (LPNM). Since the sewage sludge lacks mineral potassium (KCl), it was added to all the treatments. The LB and the LSM were conditioned with polyelectrolyte, but the LPNM was conditioned with CaOH and with FeCl3. The sewage sludge was applied in the planting rows. The effect of the different treatments on the eucalyptus trees was assessed by: six-monthly forestry inventories, leafs nutrition, estimation of monthly production of leaf fall, six-monthly estimation of leaf fall stocked in the soil, assessment of the decomposition of leaf fall in the field with decomposition bags, reflex of the sludge over the soil fertility, estimation of the biomass and the stock of nutrients and heavy metals in the trunk (stem wood + bark), in the leaves and in the fine roots of the eucalyptus trees. It was observed that the fertilization with sludge favored in average the increase of the wood volume around 65%, higher that the control (without fertilization) and similar to what observed in the treatment with mineral fertilization. The concentration of N, P, Ca, Cu, Fe and Zn in the leaves of the eucalyptus treated with the sludge, when six months old, increased significantly compared with the control. When the trees, of all the treatments were 42 months old, there was a decrease in the concentration of all nutrients in the leaves. The addition of sludge stimulated in 75% the production of leaf fall, as well as its high accumulation in the forestry soil. Consequently, the nutrients transfer was high, by the leaf fall, from the top of the trees to the litter. In general, the application of FM and of sewage sludge improved the soil fertility in the inter row (application place), mainly in the depth 0-5 cm. However, few changes were observed in the fine roots production regarding the different treatments. The sewage sludge, when conditioned in the ETE with CaOH, tends to increase the calcium stock in all the components of the system soil-plantlitter, what in long term may cause a nutritional imbalance and harmful impacts to the ecosystem. In the treatments with sewage sludge, a higher concentration of heavy metals in the leaves was observed in comparison with the control: Cu, Zn and Ni; in the leaf fall: Cu and Zn; in the soil: Cu and Zn (in the planting rows) and Zn (between-tree rows), only in the depth 0-5cm and in the fine roots: Zn and Ni. Therefore, before the application of sewage sludge in forestry plantations it is essential to know the concentration of the different elements present in it. The nutritionalmonitoring of the trees and the nutrients cycling are fundamental practices of essential importance for the good management of this residue and for the forestry farmer

O sistema estuarino de Santos, situado em Cubatão, representa um dos mais importantes exemplos brasileiros de degradação ambiental por poluição de origem industrial do país. Entre as atividades industriais geradoras de resíduos do estuário, destaca-se a indústria siderúrgica, de especial interesse nesse trabalho. O minério de ferro utilizado para a fabricação do aço é constituído essencialmente de hematita e no processo siderúrgico ele é fundido em altosfornos utilizando calcário como fundente e carvão mineral como redutor. Esse processo origina o ferro gusa tendo como impurezas carbono, silício, enxofre, fósforo, manganês etc. O ferro fundido assim obtido por meio do resfriamento desta mistura é muito quebradiço, não podendo ser utilizado, e a adição de alguns elementos como manganês, cobre e chumbo produzem aços com propriedades especiais e auxiliam na eliminação de impurezas. Os insumos utilizados nos processos siderúrgicos resultam em subprodutos que são diariamente descartados em área de manguezal que, como se sabe, são sistemas funcionalmente complexos, que se desenvolvem na zona de contato das águas marinha e fluvial. Esta área serviu para descarte de resíduos durante um período de aproximadamente 30 anos e somente a partir da década de 90 a CETESB exigiu a instalação do Aterro. Desta forma, não há possibilidade de se ter comportamento uniforme relacionado à disponibilidade iônica para o meio ambiente. Neste trabalho os dados analíticos indicaram baixa mobilidade iônica dos resíduos sólidos e que ocorrem de modo intermitente. Resultados de estudos experimentais em colunas de lixiviação, simulando água de chuva, e submetendo os resíduos à diferentes condições de força iônica, comparados com os fenômenos que ocorrem no meio natural, permitiram concluir que as águas pluviométricas têm menor influência e o fator decisivo para a disponibilidade iônica são pH e as variações dos níveis d´água em função das marés. / The estuarine system in Santos, located in Cubatão, is one of the most important Brazilian examples of environmental degradation caused by the pollution from Brazilians industries. Among the industries that dispose waste into the sewage, the steel mill stands out, and that is the reason why it the subject of this project. The iron ore used to produce the steel is a compound essentially of hematite and in its manufacture, it is casting in great temperature ovens by using calcareous to casting and coal to reduce. This process produces iron that is compound of impure carbon, silicon, sulphur, phosphorus, manganese and so on. The cast iron obtained by cooling this mixture has low resistance to break so it is no longer used, and the impurity are later removed by adding some elements as manganese, copper and lead and that produces steel with special properties. The incomes used in the manufacture of steel generates others products that are daily disposed in the fenland with no specific requires that, as known, are complex systems which develop in the contact area of the sea water and the fluvial one. In this land waste was disposed during 30 years and only after the 90´s, CETESB demanded the landfill project. So, there is no stable behavior of the availability of ions to the environment. The analytical data show low mobility of the ions and that it occurs in an intermittent way. The result from the experimental studies in a column that leached, which simulates the rain water moving through the waste in several conditions of ion strength, compared to the what happens in natural environment, concluded that the sea water and pH has lower influence and the reason for that is because the availability of ions are the variation of the water table according to tidal influence. It is proved that iron ions, manganese, copper, lead and zinc are constantly being freed which is a great hazard to the bioaccumulation once the fenland is one of the most productive ecosystems of the planet.

Os sistemas de tratamento de esgotos sanitários são considerados como requisitos básicos de infra-estrutura para as sociedades urbanas, pois possibilitam o controle e a prevenção de muitas doenças, gerando condições de higiene que promovem a saúde pública. Considerando os elementos constituintes dos efluentes urbanos e industriais, além da carga microbiológica, podem conter diversos poluentes químicos que afetam a saúde humana. Dentre os constituintes químicos, destacam-se os metais pesados que, se não devidamente removidos durante o processo de tratamento, podem causar uma poluição significativa no corpo receptor, representando um risco para a saúde humana e ambiental. Em Ribeirão Preto – SP há em funcionamento duas estações de tratamento de esgotos (ETE) sendo a ETE-Caiçara, desde o ano de 2000 e a ETE-Ribeirão Preto, desde 2002. Este estudo teve como objetivo avaliar os níveis de metais pesados em efluentes urbanos, antes e após o tratamento de esgoto pelo sistema de lodos ativados da ETE-Ribeirão Preto. Visou também avaliar os níveis de metais pesados no lodo formado durante o tratamento de esgoto pelo sistema de lodos ativados, considerando sua possível utilização para fins agrícolas. No esgoto bruto e tratado foram analisados os seguintes metais: Cd, Cr, Cu, Hg, Mn, Pb e Zn utilizando técnicas de espectrofotometria, de acordo com o tipo de metal, como: Espectrofometria de Absorção Atômica acoplado a Forno de Grafite (EAA-FG), Espectrofotometria de Absorção Atômica com Geração de Hidreto (EAA-VGA) e Espectrofotometria de Absorção Atômica de Chama (EAA-Chama). No lodo foram analisados os seguintes metais: As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, TI, V e Zn por Espectroscopia com Plasma Induzido-Espectroscopia de Massas (ICP-MS), Espectroscopia com Plasma Induzido-Espectroscopia Óptico (ICP-OES) e Espectrofometria de Absorção Atômica acoplado a Forno de Grafite (EAA-FG). Com os dados obtidos verificou-se que os níveis de metais pesados presentes nas amostras de esgoto estão dentro dos valores estabelecidos pela Resolução do Conselho Nacional do Meio Ambiente (CONAMA) nº. 357/2005 que estabelece as condições e padrões de lançamento de efluentes. Observou-se também que a remoção de metais foram muito variáveis para os diferentes metais. E as concentrações do lodo analisadas apresentaram níveis dentro dos valores estabelecidos para lodo de uso agrícola no Estado de São Paulo (CETESB, 2001). Este estudo evidencia a importância e a função de uma ETE, que é tratar os esgotos que possam causar impactos ambientais nos corpos de água que irão receber esses efluentes, e também a possível disponibilização do lodo para a agricultura, considerando que as legislações estão sendo cumpridas e apresentando, assim, informações às autoridades responsáveis pelo tratamento de esgoto do município de Ribeirão Preto-SP. / Sewage treatment systems are considered basic infrastructural requisites for urban societies, as they allow for the control and prevention of many diseases and create hygiene conditions that promote public health. Urban and industrial effluents not only carry a microbiological load, but their constituent elements can contain various kinds of chemical pollutants that affect human health. Chemical elements include heavy metals which, if removed inappropriately during the treatment process, can cause significant pollution in the receiving body and represent a risk for human and environmental health. In Ribeirão Preto – SP, Brazil, there are two sewage treatment stations (ETE), one of which is ETE-Caiçara, functioning since 2000, and the other ETE-Ribeirão Preto, since 2002. This study aimed to evaluate heavy metal levels in urban effluents before and after treatment by means of the Activated Sludge System at the ETE-Ribeirão Preto, as well as to evaluate heavy metal levels in the sludge formed during sewage treatment through the activated sludge, considering its potential use for agricultural purposes. We analyzed the following metals in raw and treated wastewater: Cd, Cr, Cu, Hg, Mn, Pb and Zn, using Graphite Furnace Atomic Absorption Spectrophotometry (AAS-GF), Atomic Absorption Spectrophotometry with Hydride Generation (AAS-HG) and Flame-Atomic Absorption Spectrophotometry (AAS-Flame). In the sludge, we analyzed the following metals: As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn, TI, V and Zn, using Inductively Coupled Plasma Mass Spectroscopy (ICP-MS), Inductively Coupled Optical Emissions Spectroscopy (ICP-OES) and Graphite Furnace Atomic Absorption Spectrophotometry (AAS-GF). The obtained data revealed that the heavy metal levels present in the wastewater samples remain within the values determined by Resolution No. 357/2005, which establishes effluent emission conditions and norms. Furthermore, we observed great variations in the removal of different kinds of metals. Metal values recorded for sludge were within the maximum permitted levels established by the Environmental Sanitation Company (CETESB), São Paulo, Brazil for agricultural use of sludge. This study evidences the importance and the function of an ETE, that is, to treat wastewater that can cause environmental impacts in the water bodies that will receive these effluents, as well as to make available sludge for agricultural use, guaranteeing that legislation is being complied with and, hence, producing information for the authorities responsible for sewage treatment in Ribeirão Preto-SP.

Estudos recentes constataram a existência de processos que permitem a atenuação natural dos contaminantes presentes nos lixiviados. O adequado entendimento destes processos pode originar benefícios possíveis de serem aplicados em aterros antigos, novos ou naqueles que ainda serão concebidos. O presente estudo avaliou o comportamento e a atenuação de contaminantes dos líxiviados no solo, por meio de experimento desenvolvido em colunas de percolação e, para a avaliação da atenuação este teste é indicado por refletir as condições naturais e as características adsortivas do solo, propiciando uma melhor simulação da atenuação. O lixiviado e o solo utilizados neste experimento são provenientes do aterro sanitário de São Carlos - SP. O solo utilizado foi caracterizado quanto à composição física, química, biológica e mineralógica para verificar o transporte do percolado nas colunas e a interação solo-contaminante. Na área do aterro foram feitas perfurações, ensaios de condutividade hidráulica e avaliação da geologia local, para conhecimento das características físicas, químicas, biológicas, mineralógicas e geológicas do solo in situ. Este foi classificado como arenoso, apresentando características físicas e químicas que não se enquadram nos parâmetros adequados para sua utilização em áreas de disposição de resíduos sólidos urbanos, pois, a capacidade de troca de cátions, superfície específica, potencial hidrogeniônico e classe textural arenosa, evidenciam que este solo possui deficiente capacidade de retenção e imobilização de contaminantes. Além disso, pela observação in situ, constata-se que a área de disposição de resíduos sólidos de São Carlos esta situado sobre rochas da Formação Botucatu, sendo que a mineralogia do solo presente no local é composta de quartzo, caulinita, goethita, hematita, gibsita e ilita. O ensaio de condutividade hidráulica indicou que o solo presente na base do Aterro sanitário não atende a valor de permeabilidade exigida por norma, o que poderá permitir a infiltração de água da chuva, aumentando a produção do lixiviado e sua movimentação no perfil, podendo atingir as águas subterrâneas. Assim, foram traçadas curvas características do transporte de contaminantes nas amostras efluentes monitoradas durante o processo de percolação, coletadas a cada 0,25 volume de poros até atingir 10,0 volume de poros percolados. As curvas características do transporte de contaminantes traçadas apresentaram baixas concentrações de Chumbo, Cádmio, Ferro, Zinco, Manganês, Cálcio, Magnésio, Cobre, Cromo nas amostras fluentes. Já o Sódio, Potássio, Cloro, Níquel e Alumínio foram preferencialmente percolados com o lixiviado, evidenciando a variação da faixa de concentração de cada elemento no percolado. Os perfis de concentração dos metais pesados mostraram que existe uma frente de contaminação. As curvas de retenção de metais no solo mostraram que a preferência de sorção apresentada pelos solos nas colunas foi : Cobre > Cádmio > Cálcio > Zinco > Magnésio > Potássio > Manganês > Fósforo > Ferro > Níquel > Alumínio. Cujos valores retidos no solo das colunas podem estar evidenciando a capacidade deste solo em reter contaminantes.O solo em questão apresentou baixo potencial para retenção dos contaminantes presentes no lixiviado, classificado como arenoso e, com características químicas que não se enquadram nos parâmetros adequados para sua utilização em áreas de disposição de resíduos sólidos urbanos. / Recent studies had found the existence of processes that allow a natural attenuation of the leachates\'s cotaminants. An adequate understanding of these processes may originate benefits, that may be applied in ancient, new or to be created landfills. This work evaluated the contaminant\'s behavior and attenuation, contaminants existing in soil\'s leaching, throughout an experiment developed in percolation columns. This is the indicated examination for evaluate the attenuation, because it reflects soil\'s natural conditions and adsorptive characteristics, providing a better simulation of it\'s attenuation. The leachate and the soil used in this experiment came from Sao Carlos-SP landfill. The used soil has been characterized as its mineralogical\'s and physical chemical-biological\'s composition, looking for the percolated\'s transportation inside the columns, and for the interaction soil-contaminant. The landfill\'s area has been several times drilled, tested as it\'s hydraulic conductivity and assessment of local geology, in order to know the physical, chemical, biological, mineralogical and geological in situ soil\'s characteristics. This, has been classified as sandy, and, by presenting chemical characteristics that does not reach the adequated value for utilization on solid urban wastes, due to the values of CTC, SE, pH, and the textural sandy class, what shows a deficient buffering capacity in retaining and immobilisating contaminants. By observation in situ, has been found that Sao Carlos\'s solids disposal waste is located over rocks from the Botucatu formation, and the mineralogy of it is composed of quartz, caulinith, goethith, hematith, gibsith an ilith. The hydraulic conductivity test has indicated that the soil in the base of the sanitary landfill does not reaches the permeability values required by the standards, what may allow rain water\'s infiltration, and raises the amount of leachate and it\'s movement onto the ground, and even the leachete to reach the underground waters. So, has been drawn the characteristics curves of the contaminant\'s transportation in the effluents samples found during the percolation process, collected by every 0,25 VP until it reaches 10,0 VP percolated. The characteristical curves of the contaminant\'s transportation drawn showed low concentrations in the effluent samples of Lead, Cadmium, Iron, Zinc, Manganese, Calcium, Magnesium, Cooper, Chromium. Also, Sodium, Potassium, Chlorine, Nickel and Aluminium had been preferencially percolated within the leachate, what evidentiates the variation in the range of concentrations of every percolated element. The concentration profiles from heavy metal\'s had shown that there is a front of contamination. The retention curves from the soil\'s retaining metal showed that the preferency for the sorption was: Cooper > Cadmium > Calcium > Zinc > Magnesium > Potassium > Manganese > Phosphorus > Iron > Nickel > Aluminium, whose values may point the soil\'s ability in retaining contaminants. The studied soil has presented low potential in retain contaminants from the leachete, and is characterized as sandy, and it\'s chemical features shall not be framed according the standards parameters to be utilized in solid urban waste\'s disposal.

Pênfigos são doenças bolhosas autoimunes com produção de autoanticorpos contra proteínas de adesão dos queratinócitos. A região nordeste (NE) do estado de São Paulo (ESP) é endêmica para o pênfigo foliáceo (PF) e pênfigo vulgar (PV). Metais pesados - chumbo (Pb), mercúrio (Hg), cobre (Cu) e zinco (Zn) - têm sido relacionados à autoimunidade e aos pênfigos. A possível contaminação do Aquífero Guarani e das bacias hidrográficas da região NE do ESP por metais pesados tem sido indagada. Objetivos. Avaliou-se: (i) cádmio (Cd), Pb, Cu, cromo (Cr), Hg, manganês (Mn) e Zn em amostras de água residencial em Ribeirão Preto (representando o Aquífero Guarani) e dos rios Pardo, Mogi-Guaçu e Sapucaí/Mirim; (ii) Pb, Cu e Zn em amostras de pacientes com PF, PV e controles; (iii) a exposição ocupacional ou por lazer às diferentes exposições aos metais pesados em pacientes e controles. Materiais e Métodos. A quantificação dos metais pesados em amostras de água, e de sangue total e de soro de 118 pacientes com pênfigo (56 PV; 62 PF) e de 135 controles foi realizada por Espectrofotometria de Absorção Atômica (com chama, forno de grafite e gerador de hidretos). Resultados. A análise do Cu (18,25 µg.L-1) no rio Sapucaí/Mirim e do Hg (0,24 µg.L-1) no rio Mogi-Guaçu mostrou valores acima da legislação vigente. Os resultados limnológicos caracterizaram a bacia do rio Mogi-Guaçu como impactada. As concentrações dos metais, em amostras de água de abastecimento urbano, apresentaram grande variação entre as residências. A concentração de Cu sanguíneo resultou maior no gênero feminino (111,9 g%; 94,5 g%). Em relação aos moradores, maiores concentrações de Zn (89,1 g%) foram observadas na cidade de Batatais, comparada a Ribeirão Preto (76,5 g%). Concentrações de Pb acima do valor de referência foram encontradas mais frequentemente no grupo PV em relação aos controles (31,1%; 15,7%, respectivamente). As concentrações de Zn foram menores entre PV e PF, comparados aos controles (75,4 g%; 80,1 g%; 83,4 g%, respectivamente). A análise multivariada mostrou maior concentração do Pb para idosos e expostos aos metais. As variáveis idade, exposição a pesticidas, exposição ocupacional, zona rural, contato com rios e concentração de Zn foram as que mais influenciaram significativamente na incidência dos pênfigos na região endêmica. Conclusões. Os metais pesados nas amostras de água obedeceram à legislação vigente, exceto Cu no rio Sapucaí/Mirim e Hg no rio Mogi-Guaçu. A etiopatogênese dos pênfigos pode estar associada à presença de Pb e à deficiência de Zn em indivíduos geneticamente predispostos. / Pemphigus are autoimmune bullous diseases with production of autoantibodies against keratinocyte adhesion proteins. The Northeast (NE) of São Paulo (ESP) is endemic to foliaceus (PF) and pemphigus vulgaris (PV). Heavy metals - lead (Pb), mercury (Hg), copper (Cu) and zinc (Zn) - have been related to autoimmunity and pemphigus. The possible contamination of the Guarani Aquifer and river basins ESP NE region by heavy metals has been inquired. Objectives. Were evaluated: (i) cadmium (Cd), Pb, Cu, chromium (Cr), mercury, manganese (Mn) and Zn in residential water samples in Ribeirão Preto (representing the Guarani Aquifer) and Pardo rivers, Mogi Guaçu and Sapucai / Mirim; (ii) Pb, Cu and Zn in samples of patients with PF, PV and controls; (iii) occupational or leisure exposure at different exposures to heavy metals in patients and controls. Materials and methods. The quantification of heavy metals in water samples, and whole blood and serum of 118 patients with pemphigus (PV 56; 62 PF) and 135 controls was performed by Atomic Absorption Spectrophotometry. Results. The analysis of Cu (0.01825 mg L-1) in the river Sapucaí / Mirim and Hg (0.00024 mg L-1) in Mogi Guaçu showed values above the legislation. Limnological results characterized the basin of the Mogi-Guaçu as impacted. The metal concentrations in urban water supply samples showed great variation between households. The blood Cu concentration resulted higher in females (111.9 g%; 94.5 g%). Compared to residents, higher Zn concentrations (89.1g%%) were observed in the city of Batatais, compared to Ribeirão Preto (76.5 g%). Pb concentrations above the reference value were found more often in PV group compared to controls (31.1%; 15.7%, respectively). Zn concentrations were lower in PV and PF, compared to controls (75.4 g%; 80.1 g%; 83.4 g%, respectively). Multivariate analysis showed higher concentrations of Pb for the elderly and exposed to metals. The variables age, exposure to pesticides, occupational exposure, rural, contact rivers and concentration of Zn were the most significant influence on the incidence of pemphigus in the endemic region. Conclusions. Heavy metals in the water samples complied with current legislation, except Cu in the river Sapucaí / Hg at Mirim and Mogi-Guaçu. The etiopathogenesis of pemphigus may be associated with the presence of Pb and Zn deficiency in genetically predisposed individuals.

Orientadores: Meuris Gurgel Carlos da Silva, Sirlei Jaiana Kleinübing / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-18T23:27:40Z (GMT). No. of bitstreams: 1 Lima_LiviaKatiadosSantos_M.pdf: 1864490 bytes, checksum: 67f5d9bfb35ec8ec36e1d0cd3334477e (MD5) Previous issue date: 2011 / Resumo: Nas últimas décadas tem-se observado sérios impactos ambientais tendo o desenvolvimento tecnológico e industrial como fonte geradora no que diz respeito ao descarte sem controle de substâncias poluentes no meio ambiente, em particular, a poluição dos recursos hídricos. Diversos problemas relacionados a crescentes despejos de metais pesados em corpos d'água pela indústria são motivo de grande preocupação, o que vem fomentando pesquisas voltadas para o desenvolvimento de técnicas de remoção destes poluentes dos efluentes industriais. Neste contexto a adsorção vem sendo avaliada como um processo viável por possuir uma vasta variedade de materiais que podem ser utilizados como adsorventes. Dentre estes materiais, as macrófitas aquáticas se destacam por possuirem características adequadas como capacidade de se desenvolverem em diferentes faixas de temperatura e pH variados, fácil cultivo e grande afinidade com íons metálicos. Neste trabalho a macrófita aquática Lemna minor foi utilizada na remoção de íons de Cr3+ de soluções aquosas utilizando um sistema em batelada. A escolha do Cr3+ foi feita a partir da observação de que grandes quantidades deste metal são utilizadas em processos industriais, principalmente naqueles relacionados ao processamento de couro. A avaliação da capacidade de bioadsorção do Cr3+ pela macrófita aquática Lemna minor foi realizada em ensaios de equilíbrio e cinéticos. Análises de espectroscopia (FTIR) mostraram a presença de grupos carboxílicos, carboxilatos e C-Cl na superfície da biomassa que participam diretamente do processo de adsorção. O modelo de Langmuir foi ajustado aos dados de equilíbrio e a capacidade máxima de adsorção foi de 11,66 mg.g-1 para uma temperatura ótima de 30 ºC. Os dados cinéticos obtidos foram analisados pelo ajuste dos modelos de pseudo-primeira, pseudo-segunda ordem e difusão intrapartícula. Porém, o modelo de pseudo-segunda ordem se ajustou mais adequadamente aos dados experimentais. Ensaios de dessorção foram também realizados com intuito de verificar a possibilidade de regeneração do adsorvente utilizando diferentes eluentes / Abstract: In the last decades serious environmental impacts can be observed as a result of the technological and industrial development which is the mainly generating source when related to uncontrolled disposal of pollutants in the environment, in particular, water resources pollution. Several problems related to increasing discharges of heavy metals in water bodies by the industry causes concern. It has promote research for the development of techniques for removing these pollutants from industrial effluents. In this context, adsorption has been evaluated as a viable process for having a wide variety of materials that can be used as adsorbents. Among these materials, the aquatics macrophyte stand to possess suitable characteristics as ability to grow in different ranges of temperature and pH varied, easy cultivation and high affinity for metal ions. In this work the Duckweed Lemna minor was used in the removal of Cr3+ from aqueous solutions using a batch system. Cr3+ metal was chosen due the observation that large amounts of this metal is used in industrial processes, particularly those related to leather processing. Assessing the ability of biosorption of Cr3+ by Duckweed Lemna minor was performed in equilibrium tests and kinetics. Spectroscopy Analysis (FTIR) showed the presence of carboxylic, carboxylate and C-Cl groups on the biomass surface. These groups directly participate in the adsorption process. The Langmuir model was fitted to the equilibrium data and maximum adsorption capacity was 11.66 mg.g-1 in an optimum temperature of 30 °C. The kinetic data were analyzed by fitting the pseudo-first, pseudo-second order and intraparticle diffusion models. However, the model of pseudo-second order fit better to experimental data. Desorption tests were also conducted in order to verify the possibility of regeneration of the adsorbent using different eluents / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

M.Tech. / The removal and recovery of heavy metals from effluents has been a subject of significant importance due the negative impact these toxic metals have on human health and the environment as a result of water and soil pollution. Precipitation is the mostly widely used wastewater treatment method because it is the most economical and easier to implement and operate on a large scale. However, traditional precipitation methods using lime, sulfides or hydroxides recover metals in the form of a sludge which is not reusable and has to be disposed in landfills creating a potential environmental hazard and resulting in loss of valuable minerals. The current focus in effluent treatment is now on the recovery and re-use of these heavy metals rather than removal and disposal. This study investigated the use of hydrazine as a reducing agent to remove and recover Ni2+, Cu2+, Co2+ and Fe2+ from effluent by reduction crystallization. In this process chemically reduced aqueous metal ions were plated on to a base substrate (nickel powder) with no electrical current required for deposition. A feasibility study was carried out to test the efficiency and find the optimum operating conditions for this method and generate an understanding of the chemical and particulate process occurring. The results obtained indicate that hydrazine is an effective reducing agent for removal and crystallization of Ni2+, Cu2+, Co2+ and Fe2+/ Fe3+ into their elemental states with nickel powder as a seeding material. Over 99 % of metals were removed from the effluent in all the systems (Ni-only, Ni-Cu, Ni-Fe and Ni-Fe). Breakage, aggregation and molecular growth were identified as the predominant mechanisms occurring during the reduction crystallization process in Ni-only, Ni-Cu, Ni- Co systems and there was evidence of nucleation in Ni-Fe solution. These finding were confirmed by analysing the scanning electron micrographs of the powder obtained. A nearly spherical structure powder with wide distribution in particle size and evidence of fragmentation was obtained in all the experimental runs. vii The residual concentrations obtained were far below the required limit for effluent discharge into sewer where 20 mg/L Ni, 20 mg/L Cu and 20 mg/L Fe and the total metal concentration of 50 mg/L for Fe, Cr, Cu, Ni, Zn and Cd is stipulated. Reduction crystallization using hydrazine as a reducing agent can be utilized for controlling environmental pollution and eliminating hazardous metals from the environment.

The Kvarntorp area, some 200 km SW of Stockholm, Sweden, is a former mining site for alum shale. Kvarntorpshögen is a refuse dump from the hydrocarbon extraction during 1940-1965. The area is also dotted by abandoned quarries, which most are water filled today. The area is divided into two watersheds; the central and the eastern. Frommestabäcken is the main watercourse flowing out of the central watershed while Frogestabäcken is the corresponding watercourse in the eastern watershed. These two watercourses have been sampled annually since 1994 by consulting companies for the municipality of Kumla. The sampling sites at Ulftorpsbäcken (main inlet to the central watershed) and at the outlet from Serpentindammssystemet (the water treatment system in the central watershed) was added to the sampling program in 1997 and 1996 respectively. Other consulting companies have sampled the groundwater around Kvarntorpshögen (in 2004) and the water in the lake Norrtorpssjön (in 2004), which is an old water filled quarry. The lake Norrtorpssjön has also been sampled as part of a project performed by Örebro University. This thesis is a compilation and evaluation of all this data but the main part will be given focused on seasonal variations. Samples have been analysed with regard to the metals Na, K, Ca, Mg, Fe, Al, Li, B, As, Cu, Ni, Zn, Co, Cr, Cd, Pb, Mo, Sr and U. Other analysed parameters were tot-N, tot-P, bicarbonate (alkalinity), sulphate, chloride and the parameters pH, electrical conductivity and COD(Mn). Samples of bottom fauna have also been collected in Frommestabäcken. Concentration of most metals increased in the surface water while passing the Kvarntorp area. High metal concentrations were found for example in some of the groundwater samples. Such high concentrations were not observed in the samples from Frommestabäcken or Frogestabäcken, indicating for example dilution of metals or immobilisation through precipitation or adsorption. Seasonal effects on the dissolution and precipitation/adsorption of compounds were observed at all annually sampled watercourses. One of these effects was the spring- and autumn circulation of the lake Norrtorpssjön. The lake forms a thermocline during summer which causes higher concentrations of metals beneath the thermocline. During circulation these concentrations mixes throughout the depth profile which affects the amount of elements that is transported from the lake via Frogestabäcken. During winter the highest concentrations of metals are expected near the surface of the lake since the surface is colder than the rest of the water mass.

Heavy metals are released into the environment either by natural processes or by anthropogenic activities. Industries such as leather tanning, textiles, metallurgical, electroplating and mining activities discharge the chromium along with other heavy metals, which causes water pollution and environmental degradation. There are many conventional methods to overcome this problem such as chemical precipitation, ion exchange, reverse osmosis, etc but, these methods have certain drawbacks like generation of secondary sludge, inefficient removal of metal ions of low concentration, high cost etc. To overcome these limitations by conventional methods, an environmental friendly method, namely bioremediation has been adopted. Bioremediation uses microorganisms, biodegradable industrial wastes, or plants to mitigate this problem. In this investigation, bacterial strains have been isolated from the soil and water samples collected from a chromite mine in Karnataka. The capability of these bacterial strains have been assessed to remediate Cr (VI) in batch experiments in order to achieve the prescribed standards of regulatory agencies, and to elucidate the mechanisms of bioremediation of Cr (VI). Additionally, using these bacterial strains, biosensors have been developed to detect Cr (VI) ions in the solution by electroanalytical techniques. The major objectives of this research investigation are: a) Isolation, characterization and identification of bacterial strains from water and soil samples obtained from a chromite mine in Karnataka. b) To study the ability of three isolated bacterial strains namely Arthrobacter sp, Exiguobacterium sp. and Micrococcus sp. to remediate Cr (VI) during growth in media, amended with different concentrations of Cr (VI) c) Delineation of the probable mechanisms of bioremediation of Cr (VI) by three bacterial strains with the aid of proteomic and metabolomic studies d) Optimization of factors influencing the bioremoval of Cr (VI) using the isolated bacterial strains as biosorbents in batch experiments. c) Elucidation of mechanisms of bioremoval of Cr (VI) at the microbe – metal interface for all three bacterial strains, adopting characterization techniques like FTIR, XPS, SEM – EDS and zeta potential measurements. d) Micrococcus sp. was chosen for the fabrication of biomodified carbon paste electrode (CPE) to sense the Cr (VI) ions using voltammetric techniques, namely cyclic voltammetry (CV) and differential pulse cathodic stripping voltammetry (DPCSV). The salient findings of this research work are highlighted as follows: Firstly, bioremediation experiments were carried out using the bacterial strains isolated from soil and water samples collected from the chromite mines of Mysore Minerals Limited, Hassan district, Karnataka, India. Initially, the characterisation of the isolated bacterial strains were carried out with respect to their biochemical aspects, antibiotic susceptibility, morphology using scanning electron microscopy and cell wall nature by Gram’s staining. The identification of the three isolated bacterial strains were accomplished by 16S rRNA method and the three bacterial strains have been identified as Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp.. The experiments were conducted to assess the potential of the isolated bacterial strains namely, Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp., for the remediation at two different concentrations of 10 mg/L and 30 mg/L of Cr (VI) ions, during cell growth i.e. using metabolically active cells of bacteria. It was found that the three bacterial strains could bioreduce toxic Cr (VI) to the less toxic Cr (III) form, by 95% to 99%, within a time span of 12 h to 120 h. In the experiment with sulphate as the competitive ion in the growing mode of the bacterial strains Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp., the percentage bioreduction of Cr (VI) to Cr (III) was not hampered. Scanning electron microscopic studies on the bacterial cells of Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp., before and after interaction with Cr (VI) showed the morphological changes after interaction with Cr (VI), as an adaptive strategy to counter the toxic effect of Cr (VI). Further, to elucidate the mechanisms of bioreduction of Cr (VI) to Cr (III) by the three bacterial strains, the proteins and metabolites were isolated from the pristine bacterial cells and Cr (VI) interacted bacterial cells. The proteins were isolated from different parts of the cells and assessed for the differential expression of proteins under Cr (VI) stress. It was found that, seven differentially expressed protein bands were observed on SDS PAGE profile of Arthrobacter sp. interacted with Cr (VI), from the soluble protein isolated from the crude extract, devoid of cell membrane. A single band of differentially expressed protein was observed in the extracellular secretion in Exiguobacterium sp. and in the case of Micrococcus sp. four differentially expressed proteins were observed in the membrane fraction of proteins. The mass spectrometry data of the differentially expressed proteins were used to identify the probable protein candidates using MASCOT search in NCBIr database. It was found that some of these proteins were a class of transport proteins and a few belong to the reactive oxygen species scavengers. These findings suggested that the bioreduction of Cr (VI) to Cr (III) involved the efflux mechanism and ROS scavenger production, to resist the toxicity of Cr (VI). The metabolite concentration profile was studied for the all three bacterial cells in the absence and presence of Cr (VI) using NMR spectroscopy. The results of this study showed an increase and decrease in the concentration of various metabolite components after interaction with Cr (VI), and this was observed in all the three bacterial strains. Some of the metabolites identified using Chenomx 8.1 metabolite library, were found to be osmoprotectants like betaine, proline etc, which combat the stress of Cr (VI). Therefore, the overall bioremediation of Cr (VI) by metabolically active bacterial cells is through bioreduction of toxic Cr (VI) to the less toxic Cr (III) form and the resistance mechanisms to overcome the toxic effect of Cr (VI) is by the efflux mechanism, production of osmoprotectants and expression of ROS scavengers. In the third part of investigation, the bioremoval of Cr (VI) ions in batch experiments using metabolically inactive cells as biosorbents, for all the three bacterial strains, were studied. The bioremediation efficiency of each bacterial strain was evaluated, considering the various parameters like effect of contact time of bacterial cells with the Cr (VI) ions, pH of Cr ion solution, biomass loading and initial concentration of Cr (VI) ion. The Cr (VI) biosorption efficiency obtained for the bacterial strains Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp. was found to be 93 %, 85 % and 100 % respectively. Apart from the biosorption of Cr (VI) by bacterial cells, the residual Cr was found to be in the form of Cr (III) ions. Therefore, complete bioremoval of Cr (VI) ions could be achieved as a combined process of biosorption and bioreduction, for all three bacterial strains, meeting the acceptable limits prescribed for Cr (VI) ion for drinking water, by regulatory agencies i.e. 0.05 mg/L of Cr (VI) ions. The biosorption of Cr ions by all the three bacterial strains were found to follow a typical Langmurian behaviour. The bioremediation process by the bacterial strains was also evaluated using suitable kinetic models and the results indicated that the bioremoval of Cr (VI) by Arthrobacter sp., Exiguobacterium sp. and Micrococcus sp. followed pseudo second order kinetics. The next aim was to ascertain the mechanism of bioremoval of Cr (VI) ions by the metabolically inactive cells. For this, different characterisation techniques were adopted that aided in the elucidation of reactions occurring at the interface of bacterial cell surface and Cr solution. The nature of interacting forces in bioremoval process was found out by desorption studies, and it was observed that only partial desorption of Cr ions was achieved from the biosorbed bacterial cells. This was further confirmed, by calculation of Gibbs free energy and the values were found to be in the range of – 25 to -32 kJ/mol, thus indicating that the process of bioremoval of Cr (VI) ions by the bacterial cells, is by chemisorption process. The variation in the charge of the bacterial cell surface, before and after interaction with chromium ions, was studied by performing zeta potential measurements as a function of pH. The surface charge of the bacterial cells alone was found to be negatively charged over a wide range of pH. Subsequent to interaction of the bacterial cells with the negatively charged oxyanions of Cr (VI) ions, the surface charge was observed to be less electronegative, which further confirmed the binding of the positively charged Cr (III) ions, formed via bioreduction on the bacterial cell surface. FTIR spectral studies revealed the functional groups involved, in bioremoval of Cr ions, present on bacterial cell surface. The functional group facilitating the bioremoval of Cr ions are –NH, -COOH and phosphate. EDS studies confirmed the Cr peak for the bacterial cells interacted with Cr ions. The oxidation state of Cr ion bound to the bacterial cell surface was determined with the help of XPS analysis. It was interesting to observe the Cr (III) peaks along with their Cr (VI) peaks. These studies provided evidence in support of the bioreduction of Cr (VI) to Cr (III) and biosorption of bioreduced Cr (III) ions onto the surface of bacterial cells, apart from the fraction present in bulk solution. The next objective was to assess the potential of Micrococcus sp. as sensor for the detection of Cr (VI) ions, using electroanalytical techniques such as, cyclic voltammetery (CV) and differential pulse cathodic stripping voltammetry (DPCSV). For this, Carbon Paste Electrode (CPE) was coated with the bacterial strain namely, Micrococcus sp and the modified electrode was used as the working electrode in a three electrode system. The developed biomodified electrode showed an approximately 3-fold increase in the sensing of Cr (VI) ion in comparison with the unmodified electrode CPE, which is attributed to the binding of Cr (VI) ions to functional groups present on the bacterial cell surface. The lower limit of detection obtained for Cr (VI) ions using CV was found to be 1 x10-4 M. The lower limit of detection was improved to 1 x 10-9 M of Cr (VI) using DPCSV.