Orientador: Antenor Pasqual / Resumo: O presente trabalho objetiva detectar a presença dos metais pesados - Cádmio (Cd), Chumbo (Pb), Níquel (Ni) e Zinco (Zn) - em estruturas biológicas como solos e plantas, em regiões consideradas como de risco para ocorrência desses elementos, provenientes da poluição ambiental emitida pelo tráfego de veículos automotores. As amostras foram coletadas ao longo de três locais do Estado de São Paulo, localizados ao longo da Rodovia Presidente Dutra, sentido São Paulo - Rio de Janeiro (km 183 - Fazenda São Judas Tadeu; km 156 - Base da Polícia Federal de São José dos Campos e Km 87 - Posto de Pedágio Moreira César). A primeira amostragem ocorreu em agosto de 1999, a segunda amostragem, em abril de 2000 e a terceira amostragem, em novembro de 2000. Para o presente estudo foram coletadas amostras de plantas e solos provenientes das margens e da "ilha" (sistema de separação de um lado do outro das pistas) da rodovia, totalizando 324 amostras, a saber: 216 amostras de solos em profundidade (0, 0-10 e 10- 20cm, no perfil do solo) e em distância da margem da rodovia (10, 20 e 30m) de cada local ao longo da rodovia; 108 amostras de plantas nos pontos de amostragem de solo na "ilha" e à distância da rodovia (15 e 30m da margem asfáltica). Para a obtenção dos extratos das amostras de solos, utilizou-se a extração por DTPA (ácido dietilenotriaminopentaacético + CaCl2 + trietanolamina), com agitação mecânica em bloco digestor; as amostras de plantas foram submetidas à digestão ácida com solução nítrico-perclórica (HNO3 + HClO4). Os extratos obtidos dos tratamentos químicos empregados nas amostras foram levados para a leitura em Espectrofotômetro de Absorção Atômica... (Resumo completo, clicar acesso eletrônico abaixo). / Abstract: The present study aims at detecting the presence of heavy metals - Cadmium (Cd), Lead (Pb), Nickel (Ni) and Zinc (Zn) - in biological structures such as soil and vegetation, in regions considered as risk-areas for the occurrence of these elements, which originate from environment pollution from automobile fuel-combustion. Samples were collected in the vicinity of three locations in São Paulo State, along the Presidente Dutra Highway, on the São Paulo - Rio de Janeiro direction (São Judas Tadeu Farm, at km 183; Federal Police Office at São José dos Campos, at km 156; and Moreira César Toll Plaza, at km 87). The first sample collection took place in August 1999; the second one, in April 2000; and the last one occurred in November 2000. For this study, plant and soil samples were collected from the highway margins and median strips (system of separation of both sides of the lanes), in a total of 324 samples, organized as follows: 216 controlled-depth (0, 0-10 and 10-20cm-deep, at the soil's profile) and controlled-distance from the margins (10, 20 and 30m) soil samples, at each location along the highway; 108 plant samples collected at the distance-controlled points of soil in the median strips collection (15 and 30m from highway margin). The extraction by DTPA (dietiletriaminopentaacetic acid + CaCl2 + trietanolamin) was used, for soil sample extracts with mechanical agitation in digesting block; plant samples were subjected to acid digestion with nitric-percloric solution (HNO3 + HClO4). Atomic Absorption Spectrofotrometrer for readings. Were used for extracts. Biological monitoring of the exposition does not exclude environmental monitoring, for both processes are valid and provide independent data which may, all in all, assess the exposition to toxic agents and their potential effects to human health and the environment... (Complete abstract, click electronic address below). / Doutor

Orientador: Patricia Soares Santiago / Banca: Marli Leite de Moraes / Banca: Valquiria da Cruz Rodrigues Barioto / Resumo: As hemoproteínas desempenham um papel vital nos organismos. Dentre elas, as hemoglobinas extracelulares gigantes (Hbs) se destacam por sua alta cooperatividade, alta estabilidade oligomérica, grande afinidade para ligação com oxigênio e resistência à oxidação. Devido estas propriedades, as Hbs apresentam um grande potencial biotecnológico, como é o caso de estudos buscando protótipos de substituição sanguínea e elaboração de biossensores. Porém, o uso das hemoglobinas gigantes em biossensores para detecção de metais pesados ainda não é encontrado na literatura, este tipo de biossensor agiliza e diminui o custo das análises de empresas e agências de fiscalização ambiental, obtendo o resultado in loco. Diante do exposto, o objetivo deste trabalho foi verificar a sensibilidade da hemoglobina de Amynthas gracilis (HbAg) com os metais cobre e cádmio em diferentes valores de pH e imobilizá-la em substrato sólido com o auxílio dos seguintes polímeros: o catiônico polietilenoimina (PEI) e o aniônico hidrocloreto de polialilamina (PAH). Os estudos por absorção ótica, espalhamento de luz (LSI), dicroísmo circular (CD) e fluorescência da interação da HbAg em função da concentração do metal pesado cobre no pH 7,0 mostraram que a concentração de 30 μmol.L-1 é uma concentração crítica onde observa-se uma maior oxidação do grupo heme, agregação e dissociação da proteína, além de alteração em suas α- hélices. No pH 5,0 foi observada oxidação do grupo heme mas sem alterações nas estruturas se... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Hemoproteins are a group of proteins that play a vital role in organisms. Among them, giant extracellular hemoglobins (Hbs) stand out for their high cooperativity, high oligomeric stability, high affinity for oxygen binding and resistance to oxidation. Due to these properties, the Hbs show a great biotechnological potential, as is the case of studies searching for prototypes of blood replacement and preparation of biosensors. However, the use of giant hemoglobins in biosensors for heavy metals detection is not yet reported on the literature, this kind of biosensors speeds up and lowers costs of analysis of companies and environmental inspection agencies, obtaining on the spot result. Thus, the aim of this work was verified the sensibility of HbAg with the metals copper and cadmium on different pH values and it's immobilization in solid surfaces with the polymers: the cationic polietilenimine (PEI) and anionic polyallylamine hydrochloride (PAH). Studies of optical absorption (UVVis), light scattering (LSI), circular dichroism (CD) and fluorescence of HbAg interaction with copper at pH 7.0 shown that 30 μmol.L-1 it's a critical concentration where observed a great oxidation of group heme, aggregation and protein dissociation as well as alteration on your α-hélices. In pH 5.0 was observed oxidation of heme group but without alterations in HbAg secondary structure and no aggregates formation. UV-Vis spectra analysis, CD, fluorescence and LSI of HbAg at different concentrations of... (Complete abstract click electronic access below) / Mestre

Metais pesados são subprodutos de atividades industriais, porém nos últimos anos os estudos têm demonstrado que mesmo em áreas não industriais, tem-se encontrado altas concentrações desses elementos. Neste estudo, mediu-se as concentrações de Zn, Ni, Cd e Pb em 20 amostras compostas de sedimentos urbanos coletadas em uma bacia hidrográfica urbana de 4,85 km² com três tipos de uso do solo (comercial/residencial, comercial e industrial), na cidade de Porto Alegre – RS. As concentrações foram determinadas por digestão ácida (EPA 3050) das frações 209, 150, 90, 63 e 45 μm seguida de espectrofotometria de emissão atômica com plasma acoplado indutivamente. As concentrações dos metais estudados foram interpoladas e representadas geograficamente utilizando Idrisi© Andes e os resultados mostram que as maiores concentrações estão localizadas na parte comercial e comercial/residencial da área de estudo, caracterizada por apresentar alto fluxo veicular na maior parte do dia, sendo considerada uma fonte potencial destes metais. Todas as concentrações estiveram acima dos valores tomados como background local e o uso do solo de cada área não representou nenhuma diferença estatística significativa (Test de Kruskall-Wallis, α = 0.05) em relação às concentrações encontradas. As concentrações foram ajustadas mediante modelos matemáticos com o diâmetro da partícula (μm), determinando que o melhor modelo para o Zn, Pb e Ni foi o exponencial e para o Cd foi o potencial. Análises mineralógicas mostraram a predominância de minerais como quartzo e feldspatos, além de minerais carbonatados, argilominerais e óxidos de ferro e manganês; o qual pode explicar a afinidade dos metais pesados pelas partículas de sedimentos urbanos. As amostras de sedimentos analisadas apresentam uma alta porcentagem de fração < 63 μm, na qual se encontram, na sua maior parte, adsorvidos os metais pesados, independentemente do local de origem da amostra; confirmando a forte correlação existente entre o tamanho da partícula e a concentração do metal. Estes resultados confirmam a presença de uma carga de poluição difusa associada ao transporte de metais pesados em sedimentos depositados em áreas urbanas impermeáveis na cidade de Porto Alegre, a qual pode impactar negativamente a saúde humana e os ecossistemas aquáticos do lago Guaíba, devido a que estes sedimentos são arrastados pelos sistemas de drenagem a este importante corpo de água da cidade. / Heavy metals are subproducts of industrial activities; however, in recent years, studies have shown that even in non-industrial areas, elevated concentrations of these elements have been found. In this study, Pb, Cd, Ni and Zn concentrations were measured in 20 composite samples of urban sediments collected in an urban hydrographic watershed of 4.85 km² with three types of soil use (commercial/residential, commercial and industrial) in the city of Porto Alegre, RS, Brazil. Concentrations were determined by acid digestion (EPA 3050) of the 209 μm, 150 μm, 90 μm, 63 μm and 45 μm fractions followed by atomic emission spectrophotometry with inductively coupled plasma. Concentrations of the metals studied were interpolated and represented geographically using Idrisi© Andes. Results show that the greatest concentrations are located in the commercial and commercial/residential part of the study area, characterized as presenting high vehicle flow most of the day, with this being considered a potential source of all theses metals. All concentrations were above that of the local background and the soil´s use not represented any statistical difference (Kruskall – Wallis Test, α = 0.05) with the founded concentrations. Metals concentrations were correlated with the particle diameters (μm), the best models were exponential for Zn, Pb and Ni, and potential model for Cd. Mineralogical analysis showed presence of quartz and feldspar, carbonated minerals, clay minerals and iron and manganese; which can explain the affinity of heavy metals by particles of urban sediments. The analyzed samples of sediments showed high percentage of the fraction < 63μm, in which, is sorved the most quantity of heavy metals, independently of the monitoring sample point, confirming the high correlation between the particle size and metal´s concentrations. These results prove the presence of a load of associated diffuse pollution to the heavy metals transport in sediments deposited in impervious urban areas in the city of Porto Alegre, which could be harmful to the human health and to the aquatic ecosystems of the Guaíba lake, due these sediments are dragged by the draining systems to this important freshwater body´s city.

Membrane technology has become a predominant process in providing one of the key components of life (water), either through water and wastewater treatment for water quality purposes or desalination as seen in Ultra-filtration, Nano-filtration, Reverse osmosis, Membrane distillation, Pervaporation, among others. With the ever-increasing demand for portable water due to population increase, constant research has focused on the improvements of the performances of the different water treatment systems including enhancing the performance of the membrane. Among all the different membrane performance enhancement techniques exploited, incorporation of filler has gained much grounds in the last decades. Traditional fillers like silica gel, activated carbon, metal oxides and zeolites are now being challenged by the recent class of mesoporous materials known as Metal Organic Frameworks (MOFs), which are built of metal ions or metal ion clusters linked together by organic ligands giving these materials tunable pore geometries and pore volume, greatly improved surface area with extraordinary adsorptive properties. The membrane incorporating MOFs demonstrate enhance performances more than the other fillers due to the good coordination of the organic moiety and polymers. The overall objective of this project is to develop and study a membrane incorporated MOFs nanofiber system vis-à-vis their applications in heavy metal contaminated water treatment, stability in aqueous media and the advantages and drawbacks of these composite membranes with regards to the quality of the water produced. The developed materials were characterized by SEM, FTIR, TEM, XPS, DSC, and TGA. The heavy metals earmarked for this study include; Lead, Mercury, Cadmium, and Zinc and were studied using flame atomic absorption spectrometry (FAAS). Upon successful fabrication of the nanofiber membranes, detailed adsorption studies were conducted (pristine MOF, pristine nanofibers, enmeshed MOFs) to establish adsorption kinetics and isotherm, which were used further to select the best performing membranes for filtration application. Two different MOFs were used, MOF808; made of Zirconium and Benzene Tricarboxylate) and MOF F300; made of Iron and Benzene Tricarboxylate) The adsorption capacities of the MOFs for the different heavy metal analyzed were; MOF 808 (Pb-170.74 mg g-1, Zn-287 mg g-1, Cd-225.05 mg g-1, Hg-276.96 mg g-1) and MOF F300 (Pb-148.13 mg g-1, Hg-229.66 mg g-1), while the membrane adsorption capacities were; PA808 (MOF 808 embedded within polyacrylonitrile (PA) nanofibers, (Pb-23.98 mg g-1, Hg-50.88 mg g-1), PA300, MOF F300 embedded within polyacrylonitrile nanofibers, (Pb-30.19 mg g-1, Hg-53.09 mg g-1). Upon activation of MOF 808 by water (hydractivation), the removal efficiency of MOF 808 was improved by 10% while the MOF membrane efficiency was increased by 30%. Filtration experiments could produce 577.5 L of treated water with a single layer of PAN/ MOF808 membrane at 0.1 bar using a 50 ppb Pb ion feed solution.

Orientador: Wanderley José de Melo / Resumo: O lodo de esgoto (LE) tem sido usado em muitos países em substituição parcial aos fertilizantes minerais. Em regiões de clima tropical a falta de estudos quanto ao comportamento dos metais pesados no solo ao longo do tempo tem limitado seu uso. O objetivo do trabalho foi avaliar os métodos de extração: Mehlich-1, USEPA 3050b e método de Jackson, quanto sua disponibilidade em função da aplicação de lodo e acúmulo dos teores de Cromo (Cr) e Chumbo (Pb) no solo. Verificou-se que, mesmo com aplicação de altas doses de Cr via LE a disponibilidade do Cr é baixa, e tem mais influência do tempo que do acréscimo do metal. O método de digestão da USEPA 3050b não apresentou sensibilidade para diferenciar o balanço do Cr em função dos tratamentos. Para extração do Cr em Latossolos de regiões de clima tropical a digestão fluorídrica juntamente com o extrator Mehlich-1 são os mais recomendados para a extração. Para o Pb o método de extração da USEPA 3050b, demonstrou de forma eficiente a diferença nos teores e no acúmulo de Pb nos diferentes tratamentos. O acréscimo de Cr e Pb via LE não influenciaram as culturas, não sendo identificados valores fitotóxicos nas plantas, nem acúmulo de Cr e Pb no grão. / Abstract: Sewage sludge (LE) has been used in many countries as a partial replacement for mineral fertilizers. In regions of tropical climate the lack of studies on the behavior of heavy metals in the soil over time has limited its use. The objective of this work was to evaluate the extraction methods: Mehlich-1, USEPA 3050b and Jackson method, as well as its availability as a function of sludge application and accumulation of Chromium (Cr) and Lead (Pb) levels in the soil. It has been found that even with high doses of Cr via LE the availability of Cr is low, and has more time influence than the addition of the metal. The USEPA 3050b digestion method showed no sensitivity to differentiate the Cr balance depending on the treatments. For extraction of Cr in Latosols of regions of tropical climate the fluoride digestion together with Mehlich-1 extractor are the most recommended for the extraction. For Pb, the USEPA 3050b extraction method efficiently demonstrated the difference in Pb levels and accumulation in the different treatments. The addition of Cr and Pb via LE did not influence the cultures, neither phytotoxic values were identified in the plants nor Cr and Pb accumulation in the grain. / Mestre

Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-04-11T19:47:35Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) igor_santos_alves.pdf: 1062838 bytes, checksum: 994f685f132399428b3bdee33d25461e (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-04-24T17:18:46Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) igor_santos_alves.pdf: 1062838 bytes, checksum: 994f685f132399428b3bdee33d25461e (MD5) / Made available in DSpace on 2017-04-24T17:18:46Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) igor_santos_alves.pdf: 1062838 bytes, checksum: 994f685f132399428b3bdee33d25461e (MD5) Previous issue date: 2016 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / A import?ncia da exist?ncia de m?todos adequados de quantifica??o de metais pesados, para a avalia??o dos teores nos solos deve ter melhor correla??o com o absorvido pelas plantas. Os objetivos deste estudo foram avaliar a disponibilidade e taxa transfer?ncia de Cd, Pb e Ni em solos contaminados; avaliar a efici?ncia dos extratores Mehlich-1, DTPA pH 7,3, Mehlich-3 e ?gua r?gia e; a correla??o entre os teores de Cd, Pb e Ni extra?dos pelos extratores e os teores na planta de milho. Os experimentos foram conduzidos em casa de vegeta??o em Diamantina MG. Os experimentos foram realizados no delineamento inteiramente casualizado no esquema fatorial 4 x 3, sendo quatro n?veis de cada metal: Cd 0, 2, 4 e 12 mg kg-1, Pb 0, 45, 90 e 270 mg kg-1 e Ni 0, 20, 40, 120 mg kg-1 e tr?s tipos de solos que foram classificados como Neossolo Quartzar?nico ?rtico t?pico (NQ), Latossolo Vermelho-Amarelo distr?fico (LVAd) e Latossolo Vermelho distr?fico (LVd) com tr?s repeti??es. O milho foi utilizado como planta indicadora. Determinaram-se a massa seca e os teores de Cd, Pb e Ni na parte a?rea e ra?zes das plantas de milho. Para aferi??o do teor de Cd, Pb e Ni no solo foram utilizados os extratores Mehlich 1, DTPA pH 7,3, Mehlich-3 e ?gua r?gia. Nos tr?s experimentos, houve maior disponibilidade dos metais no NQ em rela??o aos latossolos (LVAd e LVd), sendo o NQ onde houve maior concentra??o nas partes das plantas de milho. No experimento de Cd e Ni, nos tr?s solos, a parte a?rea apresentou maior crescimento relativo que as ra?zes. J? no experimento de Pb, devido a menor mobilidade deste metal na planta em compara??o ao Cd e Ni, houve maior concentra??o de Pb nas ra?zes que na parte a?rea. Os maiores teores tanto de Cd, quanto Pb e Ni na parte a?rea e ra?zes ocorreram no NQ, sendo o solo onde ocorreu maior transloca??o dos tr?s metais para a parte a?rea. Nos tr?s experimentos, os extratores utilizados tiveram boa correla??o com os teores absorvidos pelas plantas e as extra??es por DTPA pH 7,3 apresentaram melhor correla??o com os teores de Cd e Pb tanto nas ra?zes quanto na parte a?rea. Com rela??o ao Ni, os extratores Mehlich-1 e ?gua r?gia foram os que apresentaram maior correla??o com os teores absorvidos pelas plantas. Os metais pesados Cd, Ni e Pb apresentam maior mobilidade em solos com baixo teor de argila, podendo ser mais facilmente absorvido pelas plantas. O crescimento das plantas pode influenciar a toxidez por metais, de modo que, quanto maior o crescimento menor o efeito t?xico do metal, como verificado nos tr?s experimentos. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Produ??o Vegetal, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / The importance of the existence of adequate methods of quantification of heavy metals for the evaluation of soil concentrations should have a better correlation with that absorbed by the plants. The objectives of this study were to evaluate the Cd, Pb and Ni availability and transfer rate in contaminated soils, to evaluate the efficiency of the extractors Mehlich-1, DTPA pH 7.3, Mehlich-3 and, aqua regia and, the correlation between the Cd, Pb and Ni concentrations extracted by the extractors and the concentrations in the corn plant. The experiments were conducted in a greenhouse in Diamantina, Minas Gerais State, Brazil. The experiments were carried out in a completely randomized design in the 4 x 3 factorial scheme, with four rates of each metal: Cd 0, 2, 4 and 12 mg kg-1, Pb 0, 45, 90 and 270 mg kg-1 and Ni 0, 20, 40, 120 mg kg-1, and three soil types that were classified as Typic Quartzipsamment (TQ), Xantic Hapludox (XH) and Rhodic Hapludox (RH) with three replicates. Corn was used as the indicator plant. The dry mass and the Cd, Pb and Ni concentrations were determined in the shoot and roots of corn plants. The Mehlich 1, DTPA pH 7.3, Mehlich-3 and aqua regia extractors were used to measure the Cd, Pb and Ni concentrations in the soil. In three experiments, a greater availability of metals in TQ regarding latosols (XH and RH), the TQ where there was a higher concentration in parts of corn plants. In the experiment of Cd and Ni in the three soils, the shoots had higher relative growth than the roots. In the Pb experiment, due to the lower mobility of this metal in the plant compared to Cd and Ni, a higher Pb concentration in roots than in shoots. The highest concentrations both of Cd, Pb and Ni as in shoots and roots occurred in TQ, and the soil where higher translocation of the three metals to shoots. In three experiments, the extractors used correlated well with the concentrations absorbed by plants and extractions by DTPA pH 7.3 showed better correlation with Cd and Pb concentration in the roots and shoots. With respect to Ni, the Mehlich-1 extractor and aqua regia showed the highest correlation with the concentrations absorbed by plants. Heavy metals Cd, Ni and Pb have greater mobility in soils with low clay content, and can be more easily absorbed by plants. Plant growth can influence the toxicity of heavy metals, so that the higher the lower the toxic effect growth of the metal, as seen in the three experiments.

Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2018-03-15T20:14:01Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) amanda_dias_araujo.pdf: 4866060 bytes, checksum: 4bf20df489807647557baa1fee5ae8ac (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-03-29T12:42:50Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) amanda_dias_araujo.pdf: 4866060 bytes, checksum: 4bf20df489807647557baa1fee5ae8ac (MD5) / Made available in DSpace on 2018-03-29T12:42:50Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) amanda_dias_araujo.pdf: 4866060 bytes, checksum: 4bf20df489807647557baa1fee5ae8ac (MD5) Previous issue date: 2017 / Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) / O garimpo denominado Areinha est? inserido na bacia hidrogr?fica do rio Jequitinhonha, cujas ?guas drenam ?reas de garimpos que influenciam diretamente na qualidade do recurso h?drico. A ?rea de pesquisa possui uma extens?o de aproximadamente 9 quil?metros, ?rea que est? sob os cuidados da Cooperativa Regional de Garimpeiros de Diamantina. A pesquisa avalia os par?metros para os metais c?dmio, cobre, ferro, mangan?s, n?quel, chumbo e zinco, analisando a concentra??o e a posterior compara??o com a legisla??o do CONAMA 344/04. Foram analisados par?metros f?sico-qu?mico potencial hidrogeni?nico (pH) e temperatura da ?gua, e comparadas com o CONAMA 357/05, visando inferir um alerta sob os riscos ? sa?de que da exposi??o direta a esses metais pode causar na popula??o. Foram coletadas um total de 13 amostras, analisados pela t?cnica da espectrometria de absor??o at?mica por chama. A quantifica??o de c?dmio n?o apresentou concentra??es que est?o acima dos N?veis I e II do CONAMA 344/04. O cobre, os valores obtidos ultrapassam o N?vel I, no Ponto 3 Extra (84,3 mg/kg), e o Ponto 1 Extra (362,78 mg/kg), excedendo o N?vel II. Para o ferro e mangan?s, o CONAMA 344/04 n?o apresenta valores guia. O n?quel, dos 13 pontos amostrados, apenas um ultrapassa a legisla??o, s?o eles o Ponto 3 Extra (18,4 mg/kg), ultrapassando o N?vel I. Para o chumbo, seis pontos est?o entre o N?vel I (35,0 mg/kg) e o N?vel II (91,3 mg/kg), e um ponto ultrapassa o N?vel II. Para o zinco nenhum dos treze pontos violou a legisla??o vigente. Nas ?reas em que os pontos ultrapassam a legisla??o, geralmente, encontram-se em bacias de reten??o de rejeitos, o que ocasiona a deposi??o de sedimentos ao logo do tempo, aumentando, assim, esse valor. Os valores encontrados para pH e temperatura foram comparados ? Resolu??o do CONAMA 357/05 e indicam um ambiente dentro da faixa da Resolu??o (pH de 6,0 a 0,9), e temperatura abaixo dos 40 ?C. A modifica??o nas atividades de garimpo, de manuais para mecanizadas, intensificou o impacto ambiental negativo nessa regi?o, devido a necessidade de removerem grandes quantidades de sedimentos para a extra??o do ouro e diamante. Os pontos citados acima localizam-se em bacias de reten??o de rejeitos, ambientes considerados fr?geis, j? que qualquer enchente no leito do rio, pode ocasionar o rompimento da mesma, e a distribui??o desse material no curso d??gua. / Disserta??o (Mestrado Profissional) ? Programa de P?s-Gradua??o em Sa?de, Sociedade e Ambiente, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The mining called Areinha is inserted in the area of the Jequitinhonha river, whose waters drain mining areas that directly influence the quality of the water resource. The research area has an extension of approximately 9 kilometers, an area that is under the care of the ?Cooperativa Regional de Garimpeiros de Diamantina?. The research evaluates the parameters for the metals cadmium, copper, iron, manganese, nickel, lead and zinc, analyzing the concentration and the subsequent comparison with the legislation of CONAMA 344/04. Physical-chemical parameters were analyzed for potential hydrogenation (pH) and water temperature, and compared to CONAMA 357/05, aiming to infer an alert under the health risks that direct exposure to these metals can cause in the population. A total of 13 samples were collected, analyzed by flame atomic absorption spectrometry. The quantification of cadmium did not present concentrations that are above Levels I and II of CONAMA 344/04. Copper values exceed Level I at Point 3 Extra (84.3 mg / kg) and Point 1 Extra (362.78 mg/kg), exceeding Level II. For iron and manganese, CONAMA 344/04 does not present guide values. Nickel of the 13 points sampled, only one exceeds the legislation, they are Point 3 Extra (18.4 mg/kg), exceeding Level I. For lead, six points are between Level I (35.0 mg/Kg) and Level II (91.3 mg/kg), and one point exceeds Level II. For zinc, none of the thirteen points violated the current legislation. In areas where points exceed legislation, they are usually found in tailings retention basins, which causes the deposition of sediment over time, thereby increasing the value. The values found for pH and temperature were compared to the Resolution of CONAMA 357/05 and indicate an environment within the Resolution range (pH 6.0 to 0.9) and temperature below 40 ?C. The change in mining activities from manuals to mechanized intensified the negative environmental impact in this region due to the need to remove large amounts of sediment for the extraction of gold and diamond. The points mentioned above are in retention basins of rejects, environments considered fragile, since any flood in the river bed, can cause the breakage of the same, and the distribution of this material in the watercourse.

Oyster shells are normally applied in wastewater treatment in the form of a powder; but the possibility of whole oyster shells removing metal ions in stormwater has not been investigated. The objectives of this research are to assess the application of whole oyster shells for removing metals in low concentration solutions and to explore the influence of the following factors: surface area of shells, initial concentration and exposure time, on removal efficiency. Experimental results demonstrated very good removal efficiency by oyster shells for removing copper, followed by cadmium and zinc; but was not effective in hexavalent chromium removal. Up to 70% removal can be reached in just one hour for copper with initial concentrations of 0.2ppm with 550cm2 of surface area (SA) of shells in a beaker experiment treating two-liter solutions (with an accompanying pH increase from 5 to 6.42). A removal efficiency (RE) of 57.7% and 33.3% was found for cadmium and zinc, respectively, with one day contact using shells of 300cm2 SA treating one liter of the lowest concentration solution; while only 14.3% was achieved for chromium under the same conditions. Mid-scale experiments with continuous inflow based on the 6-hour Saanich Design Storm demonstrated an 85.5% and an 83.9% RE of cadmium and copper in one day’s worth of contact time. There was no removal but in fact an increase in chromium and zinc was found for the mid-scale experiment. There was a positive relationship between initial concentration (IC) and removal efficiency for copper and zinc, but a negative relationship for chromium, while no relationship was found for cadmium. Up to 80% of copper can be removed at IC of 2.4ppm compared to 60% with IC of 0.65ppm with same amount of shells (by surface area). RE of 70%, 75% and 83% was observed for IC of 0.3ppm, 0.58ppm and 1.07ppm for zinc, respectively, with 154 cm2 SA. When IC of chromium is reduced from 1 ppm to 0.2ppm, RE tends to drop from 60% to 26%. There was also a positive relationship between SA and RE, and ET and RE. However, after a certain exposure time, increase in RE was negligible and sometimes, desorption would occur. Additionally, when the difference in surface area is small, the influence of this factor on RE was also small. When treating certain ranges of solution concentration, the effect of surface area on RE is difficult to distinguish. Moreover, the role of HRT in stormwater systems was not clearly found. / Graduate

Metais pesados são subprodutos de atividades industriais, porém nos últimos anos os estudos têm demonstrado que mesmo em áreas não industriais, tem-se encontrado altas concentrações desses elementos. Neste estudo, mediu-se as concentrações de Zn, Ni, Cd e Pb em 20 amostras compostas de sedimentos urbanos coletadas em uma bacia hidrográfica urbana de 4,85 km² com três tipos de uso do solo (comercial/residencial, comercial e industrial), na cidade de Porto Alegre – RS. As concentrações foram determinadas por digestão ácida (EPA 3050) das frações 209, 150, 90, 63 e 45 μm seguida de espectrofotometria de emissão atômica com plasma acoplado indutivamente. As concentrações dos metais estudados foram interpoladas e representadas geograficamente utilizando Idrisi© Andes e os resultados mostram que as maiores concentrações estão localizadas na parte comercial e comercial/residencial da área de estudo, caracterizada por apresentar alto fluxo veicular na maior parte do dia, sendo considerada uma fonte potencial destes metais. Todas as concentrações estiveram acima dos valores tomados como background local e o uso do solo de cada área não representou nenhuma diferença estatística significativa (Test de Kruskall-Wallis, α = 0.05) em relação às concentrações encontradas. As concentrações foram ajustadas mediante modelos matemáticos com o diâmetro da partícula (μm), determinando que o melhor modelo para o Zn, Pb e Ni foi o exponencial e para o Cd foi o potencial. Análises mineralógicas mostraram a predominância de minerais como quartzo e feldspatos, além de minerais carbonatados, argilominerais e óxidos de ferro e manganês; o qual pode explicar a afinidade dos metais pesados pelas partículas de sedimentos urbanos. As amostras de sedimentos analisadas apresentam uma alta porcentagem de fração < 63 μm, na qual se encontram, na sua maior parte, adsorvidos os metais pesados, independentemente do local de origem da amostra; confirmando a forte correlação existente entre o tamanho da partícula e a concentração do metal. Estes resultados confirmam a presença de uma carga de poluição difusa associada ao transporte de metais pesados em sedimentos depositados em áreas urbanas impermeáveis na cidade de Porto Alegre, a qual pode impactar negativamente a saúde humana e os ecossistemas aquáticos do lago Guaíba, devido a que estes sedimentos são arrastados pelos sistemas de drenagem a este importante corpo de água da cidade. / Heavy metals are subproducts of industrial activities; however, in recent years, studies have shown that even in non-industrial areas, elevated concentrations of these elements have been found. In this study, Pb, Cd, Ni and Zn concentrations were measured in 20 composite samples of urban sediments collected in an urban hydrographic watershed of 4.85 km² with three types of soil use (commercial/residential, commercial and industrial) in the city of Porto Alegre, RS, Brazil. Concentrations were determined by acid digestion (EPA 3050) of the 209 μm, 150 μm, 90 μm, 63 μm and 45 μm fractions followed by atomic emission spectrophotometry with inductively coupled plasma. Concentrations of the metals studied were interpolated and represented geographically using Idrisi© Andes. Results show that the greatest concentrations are located in the commercial and commercial/residential part of the study area, characterized as presenting high vehicle flow most of the day, with this being considered a potential source of all theses metals. All concentrations were above that of the local background and the soil´s use not represented any statistical difference (Kruskall – Wallis Test, α = 0.05) with the founded concentrations. Metals concentrations were correlated with the particle diameters (μm), the best models were exponential for Zn, Pb and Ni, and potential model for Cd. Mineralogical analysis showed presence of quartz and feldspar, carbonated minerals, clay minerals and iron and manganese; which can explain the affinity of heavy metals by particles of urban sediments. The analyzed samples of sediments showed high percentage of the fraction < 63μm, in which, is sorved the most quantity of heavy metals, independently of the monitoring sample point, confirming the high correlation between the particle size and metal´s concentrations. These results prove the presence of a load of associated diffuse pollution to the heavy metals transport in sediments deposited in impervious urban areas in the city of Porto Alegre, which could be harmful to the human health and to the aquatic ecosystems of the Guaíba lake, due these sediments are dragged by the draining systems to this important freshwater body´s city.

Neste estudo, avaliou-se a ocorrência de metais pesados em ambiente fluvial sob influência de curtumes - a bacia hidrográfica dos rios Cadeia e Feitoria (RS, Brasil), focalizando sua origem, distribuição e mobilidade potencial. Trimestralmente, entre julho/1999 e abril/2000, analisaram-se metais e parâmetros complementares em amostras de água e sedimento coletadas em dez locais. Após identificar os contaminantes e locais críticos (cromo e mercúrio, no trecho inferior do rio Feitoria), avaliaram-se também perfis sedimentares verticais e tecido muscular de peixes de fundo (Rineloricaria). As análises de água seguiram recomendações do Standard Methods, enquanto as demais basearam-se principalmente em métodos da agência de proteção ambiental dos Estados Unidos (USEPA) ou Comunidade Européia, buscando prever a disponibilidade potencial dos metais. Utilizou-se estatística descritiva e multivariada na análise dos dados, visando sintetizar informações e subsidiar a futura elaboração de um atlas ambiental. Rastreou-se o risco potencial de danos crônicos não carcinogênicos à saúde humana por ingestão de água e peixes contaminados, conforme metodologia recomendada pela USEPA.A ocorrência de metais vinculou-se a contribuições naturais e antropogênicas, representadas principalmente pela intemperização de basaltos e atividades de curtumes. Influenciada pela proximidade dos curtumes e flutuações na vazão, a qualidade das águas diminuiu ao longo dos rios e no período de menor disponibilidade hídrica (janeiro). Os teores de metais nas águas obedeceram aos padrões da legislação brasileira, exceto para alumínio, ferro e eventualmente manganês. Considerando a ingestão de água em cenário hipotético de alta exposição aos metais estudados (água bruta, picos de contaminação, cromo na forma hexavalente), verificouse uma potencial ausência do risco de efeitos adversos à saúde humana. Entretanto, a área sob maior influência de curtumes demonstrou considerável aumento desse risco, em comparação aos locais de referência. Nos sedimentos, as concentrações de alumínio, cobre, ferro, níquel, manganês, titânio e zinco pareceram refletir níveis basais, ao contrário de cromo e mercúrio, enriquecidos no trecho inferior da bacia. Além de condições de avançado intemperismo, os perfis sedimentares indicaram que as descargas de metais antropogênicos poderiam não estar restritas a atividades pretéritas. A partição dos metais nas fases geoquímicas dos sedimentos revelou maior mobilidade potencial do manganês em toda a bacia, seguido por cromo, na área de concentração de curtumes (predominantemente vinculado à fração oxidável). Ainda que em teores abaixo do recomendado pela Organização Mundial da Saúde (0,5 μg/g), observou-seacúmulo de mercúrio nos peixes, indicando condições ambientais favoráveis à sua metilação. Para reduzir efeitos tóxicos crônicos não carcinogênicos à saúde humana por exposição ao mercúrio, um eventual consumo do peixe estudado deveria ser restrito a 32 g/dia no trecho contaminado. Mesmo não sendo detectado nos peixes, o considerável aumento do teor de cromo nos sedimentos do trecho inferior da bacia sugeriu possibilidade de ocorrerem localmente outros efeitos prejudiciais à biota aquática. Uma potencial mobilização do cromo retido nos sedimentos estaria vinculada às condições redox do meio, enquanto o enxofre poderia condicionar a biodisponibilidade do mercúrio. Estudos posteriores são necessários para melhor entendimento dos processos de mobilização e bioacumulação de metais na área de estudo, envolvendo organismos de diferentes níveis tróficos. / This study evaluated the occurrence of heavy metals in a fluvial environment under the influence of tanneries – the Cadeia and Feitoria rivers watershed (RS, Brazil), phocusing their origin, distribution, and potential mobility. Every three months, between July 1999 and April 2000, selected heavy metals and ancillary parameters were analyzed in water and sediment samples taken at ten sites. After identifying the contaminants and sites of concern (chromium and mercury at the lower reach of Feitoria River), vertical sediment profiles and bottom-fish tissue (Rineloricaria) were also evaluated. Water analyses followed recommendations of the Standard Methods, while the remaining analyses were based mainly on methods from the Environmental Protection Agency of the United States (USEPA) and European Community, searching for estimating the potential availability of metals. Descriptive and multivariate statistics were applied to water and sediment data sets, in order to obtain a synthesis of the environmental diagnosis, and to support the elaboration of an environmental atlas. A risk assessment methodology recommended by USEPA was conducted at a screening level, in order to estimate the potential non-carcinogenic toxic effects to the human health arising from life-time consumption of contaminated water and fish.The results revealed that the heavy metals originate from natural and anthropogenic contributions, mainly resultant from the weathering of basalt rocks and tannery activities. The water quality decreased along both rivers, and during the dry period (January), showing the influence of tannery plants vicinity and flow variations. Except for iron, aluminum, and eventually manganese, heavy metal contents in water were generally in agreement with Brazilian standards. Despite considering the ingestion of water in a hypothetical scenario of high human exposure to the selected metals (untreated water, peaks of contamination, chromium in the hexavalent form), the risk screening indicated a potential absence of adverse toxicological health effects. However, in comparison to the reference sites, this risk considerably increased at the lower reach of Feitoria River, the most affected by tanneries. Concerning sediments, aluminum, copper, iron, nickel, manganese, titanium, and zinc concentrations appeared to reflect the base levels, in opposition to chromium and mercury, which were enriched in the lower part of the basin. The sediment profiles revealed an advanced weathering-stage, and also indicated that the anthropogenic discharges of heavy metals might not be strictly resultant from past activities. The partition of heavy metals among the sediment geochemical phases showed higher mobility of manganese along the basin, followed by chromium in thearea most affected by tanneries (predominantly associated to the oxidizable fraction). Although occurring in levels below the World Health Organization threshold for human consumption (0.5 μg/g), the accumulation of mercury in fish indicated that the prevailing environmental conditions could favor its methylation. Considering the methodology of risk assessment, an eventual consumption of the investigated fish should be restricted to 32 g/day at the lower reach of Feitoria River, in order to reduce the occurrence of non-carcinogenic toxic effects to the human health, arising from oral exposure to mercury. Although chromium was not detected in fish tissue, its considerable enrichment in sediments from the lower part of the basin indicated a potential occurrence of other hazardous effects on aquatic organisms. A potential mobilization of chromium from the contaminated sediments would be associated to the prevailing redox conditions, while the sulfur cycling could influence the bioavailability of mercury. Further research with organisms from distinct trophic levels is needed, in order to better understand the metal bioaccumulation processes that are taking place in the study area.