Le sélénium (Se) est un élément chalcogène avec un domaine de concentration étroit entre essentialité et toxicité. La toxicité est principalement liée à la spéciation chimique du Se qui évolue en fonction des conditions redox du milieu. Les formes oxyanioniques de Se, le sélénite (Se [IV], SeO32-) et le séléniate (Se [VI], SeO42-), sont solubles dans l'eau, biodisponibles et toxiques. En revanche, le sélénium élémentaire, Se(0), est insoluble et moins toxique. Néanmoins, les nanoparticules du Se(0) sont potentiellement dangereuses pour certains groupes des mollusques (comme les bivalves) et aussi pour les poissons. En outre, lorsque le Se(0) est rejeté dans les écosystèmes aquatiques, sa ré-oxydation jusqu'au sélénite et séléniate peut se produire. Le sélénium élémentaire d'origine biogénique Se(0) a été produit par la réduction de SeO42- dans des conditions anaérobies en utilisant un inoculum microbien mixte (boues granulaires) et par la réduction de SeO32- dans des conditions aérobies en utilisant une culture bactérienne pure (une nouvelle souche de Pseudomonas moraviensis identifiée et caractérisée pour la première fois dans cette thèse). Les deux types de Se(0) ont montré une forte stabilité colloïdale dans l'écart de pH variant de 2 à 12. La stabilité colloïdale est due à la charge négative (-15 mV à -30 mV) de la couche de biopolymère qui entoure Se(0) et à la taille nanométrique des particules de Se(0). La taille des particules de Se(0) produite par la boue anaérobie granulaire se situait entre 50 et 300 nm, avec une taille moyenne de 166 nm. A l'inverse, les nanoparticules de Se(0) produites par Pseudomonas moraviensis stanleyae sont caractérisées par un diamètre plus faible (~ 100 nm).Compte tenu des risques pour l'environnement engendrés par le relargage du Se(0) biogénique, des mesures appropriées doivent être mises en œuvre pour la séparation solide-liquide en utilisant une technologie efficace. Le potentiel de séparation solide-liquide de Se(0) généré a été évaluée par centrifugation, filtration, coagulation-floculation et électrocoagulation. Alors que toutes les approches présentent des rendements de séparation de Se(0) variables, l'électrocoagulation en utilisant des électrodes sacrificielles de fer a montré l'efficacité d'élimination le plus élevée (97%) / Selenium (Se) is a chalcogen element with a narrow window between essentiality and toxicity. The toxicity is mainly related to the chemical speciation that Se undergoes under changing redox conditions. Se oxyanions, namely selenite (Se[IV], SeO32-) and selenate (Se[VI], SeO42-), are water-soluble, bioavailable and toxic. In contrast, elemental selenium, Se(0), is solid and less toxic. Nevertheless, Se(0) nanoparticles are potentially harmful as particulate Se(0) has been reported to be bioavailable to filter feeding mollusks (e.g. bivalves) and fish. Furthermore, Se(0) is prone to re-oxidation to toxic SeO32- and SeO42- when discharged into aquatic ecosystems. Biogenic Se(0) under investigation was produced by the reduction of Na2SeO4 under anaerobic conditions using a mixed bacterial inoculum (anaerobic granular sludge) and through the reduction of Na2SeO3 under aerobic conditions using a pure microbial culture (Pseudomonas moraviensis stanleyae, a novel strain identified and characterized for the first time herein). Both types of Se(0) showed strong colloidal stability within the 2-12 pH range. The colloidal stability is caused by the negatively charged (-15 mV to -30 mV) biopolymer layer covering biogenic Se(0) particles and by their nanometer size. The particle size of Se(0) produced by anaerobic granular sludge ranged between 50 and 300 nm, with an average size of 166 nm. Conversely, the Se(0) particles produced by Pseudomonas moraviensis stanleyae are characterized by a lower diameter (~ 100 nm).The solid-liquid separation potential of Se(0) was assessed by centrifugation, filtration, coagulation-flocculation and electrocoagulation. While all approaches can bring about Se(0) removal from suspension with various degrees of success, electrocoagulation using iron sacrificial electrodes showed the highest removal efficiency (97%). Because biogenic Se(0) is harmful to the environment, appropriate measures must be implemented for the solid-liquid separation using an efficient technology

Este estudo objetivou comprovar a influência da agricultura na presença de metais pesados (Cádmio, Cobre, Chumbo, Manganês, Mercúrio, Níquel e Zinco) nas águas do rio Pardo, constatada pela CETESB, no período compreendido entre 1978 a 1997, na região de Ribeirão Preto, cujo desenvolvimento econômico é decorrente da agricultura e de indústrias de açúcar e álcool. O trecho do rio estudado, além da presença de esgoto sanitário sem tratamento, não apresenta fontes geradoras de metais pesados, próprias de regiões altamente industrializadas ou mesmo de áreas de extração de minerais metálicos. Verificou-se que as concentrações destes metais crescem com o aumento da vazão do rio, indicando a influência da carga difusa. Buscou-se determinar a origem dessa carga, avaliando esses metais, com exceção do mercúrio em amostras de solo agricultado, em resíduos orgânicos das usinas de açúcar e álcool aplicados no solo e em sedimentos. Os resultados mostraram que essas áreas agrícolas apresentam concentrações de metais maiores que aquelas naturalmente existentes no solo estudado, certamente pelo uso de insumos agrícolas. Nos resíduos industriais destacaram-se o Cobre e o Chumbo, cuja origem deve ser investigada. Os sedimentos também revelaram concentrações consideráveis de metais, cuja biodisponibilidade deve ser avaliada. Conclui-se ser a atividade agrícola uma das origens da presença dos metais estudados nas águas do rio Pardo. Contudo, é necessário realizar uma avaliação dos fertilizantes, corretivos do solo, biossólidos industriais e defensivos agrícolas comumente utilizados na área e dos vegetais produzidos, considerando que a acidez do solo local favorece à absorção de metais pelos vegetais cultivados. / The objective of the study was to establish the relationship between agricultural activities and the presence of some heavy metals (cadmium, copper, lead, manganese, mercury, nickel and zinc) in Pardo river, using data frorn CETESB river samplings during the period 1978 to 1997. The samples were taken from the region of Ribeirão Preto country, from state of São Paulo. The development and economical activities are based on agriculture and sugarcane and alcohol industries. Domestic wastes with no treatment are discharged into the river, but this can not be considered as a significant source of heavy metals, normally occurring in the industrialized or mining areas. It was verified that the concentrations of these metals increased with the stream flow increase, indicating the influence of spread charge. It was tried to determine the origin of this charge, evaluating these metals, except mercury, in agricultural soil samples, in organic residues from sugar and alcohol industries applied to the soils and in sediments. The results showed that the agricultural areas presented metals concentrations greater than the naturally existent in the studied soil, certainly by the agricultural amendments. In the industrial residues stood out cooper and lead, which origin must be investigated. The sediments also presented considerable concentrations of metals, which bioavailability must be estimated. It was concluded that the agricultural activity is one of the origins of the studied metals presence in the Pardo river. Althought, it is necessary to evaluate the fertilizers, soil amendments, industrial biosolids and agricultural pesticides commonly used in the area and the vegetables produced, considering that the acidity of the local soil collaborates to metals uptake by the vegetables.

DOMINGUEZ, Danielle Xanchão. Avaliação dos riscos ambientais associados à utilização agrícola de lodo de esgoto como condicionador e fertilizante de solo, 2014. Tese (Doutorado) Programa de Pós-Graduação em Ciência Ambiental (PROCAM), Universidade de São Paulo, São Paulo, 2014. 116 f. Esta tese tem como objetivo avaliar os riscos ambientais envolvidos nos processos de utilização agrícola de lodos de esgoto, como condicionador e fertilizante de solo, ao longo de cinco anos. O presente estudo está inserido em uma pesquisa mais ampla e conduzida desde 1998, a qual, por sua vez, constitui parte de um projeto interdisciplinar de longo prazo e que reúne diversas instituições de pesquisa. A utilização de lodo de esgoto na agricultura, quando realizada dentro de critérios seguros, agrega baixo custo e impacto ambiental positivo. Ao promover o retorno dos nutrientes ao solo, tal prática se configura como uma alternativa adequada para sua disposição final. O trabalho baseia- se na análise do efeito da aplicação de lodo de esgoto na acumulação de metais pesados e na disponibilização de nutrientes em um solo classificado como Latossolo. Foram analisados os parâmetros pH, capacidade de troca catiônica (CTC), carbono orgânico e os teores dos macronutrientes: Nitrogênio (N), Fósforo (P) e Enxofre (S). Os metais considerados micronutrientes para as plantas: Cobre (Cu), Ferro (Fe), Manganês (Mn), Zinco (Zn) e Níquel (Ni) e os metais pesados: Cádmio (Cd), Cromo (Cr) e Chumbo (Pb) foram analisados por dois métodos de extração simples (Mehlich 1 e DTPA) e também pelo método da extração sequencial. Verificou-se que o uso de lodo de esgoto influenciou as propriedades do solo, que tiveram significativas mudanças em quase todos os parâmetros analisados. O estudo aponta, entre outras conclusões, que o uso de lodo é importante para o aumento do teor de fósforo (P) em solos tropicais. Observou-se também que o conteúdo de metais pesados foi maior nas parcelas fertilizadas com lodo de esgoto proveniente da ETE de Barueri (esgoto domestico e industrial) em relação às áreas tratadas com esgoto oriundo da ETE de Franca (esgoto predominantemente doméstico). Observou-se também que as parcelas que receberam aplicações de lodo superiores à estabelecida pela legislação apresentaram alterações significativas na concentração de enxofre, nitrogênio, fósforo, micronutrientes e metais pesados, aumentando os riscos ambientais associados a tal prática. Tal conjunto de resultados ratifica a hipótese de que o uso do lodo de esgoto como fertilizante e condicionador de solo, pode ser uma prática adequada e segura. Entretanto, tal procedimento vem exigir não apenas o atendimento aos requisitos legais, sobretudo a taxa de aplicação máxima de lodo de esgoto permitida, como também o monitoramento frequentemente a fim de evitar impactos negativos. / The purpose of this research was to identify and assess the risks related to the use of sewage sludge on agricultural land, analyzing the accumulation of heavy metals and the availability of nutrients in a soil classified as Oxisol. The parameters pH, CEC (cation exchange capacity), organic carbon and the levels of macronutrients N (nitrogen), P (phosphorus) and S (Sulfur) were analyzed. Single and sequential extraction procedures were applied to measure the metals considered micronutrients to plants - Cu (Copper), Fe (iron), Mn (Manganese), Zn (zinc), and Ni (nickel) - and the heavy metals: Cd (Cadmium), Cr (chromium) and Pb (Lead ). The results obtained confirm the hypothesis that the use of sewage sludge can be adequate and safe. However, for large-scale adoption of this procedure, it is recommended not only require compliance to legal requirements, specially the maximum amount of sewage sludge application permitted, as well as frequent monitoring are recommended in order to avoid potential negative impacts.

Este trabalho objetivou estudar a síntese de zeólita NaA sob condições hidrotérmicas e aplicála na adsorção de metais pesados. Para a síntese de zeólita NaA, caulim do município de Ipixuna, Pará, foi calcinado a 700 °C por 3 horas para obtenção de metacaulim e usado como fonte de sílica e alumina. Para efeito de comparação, cloreto de alumínio e metassilicato de sódio também foram utilizados na síntese de zeólitas como precursores de Si e Al. A influência da alcalinidade na síntese dos produtos zeolíticos foi avaliada utilizando-se diferentes concentrações de NaOH. Todas as sínteses foram realizadas a 110 °C em autoclaves. Visando à compreensão da influência do tempo na quantidade e tipo de fase formada, foram realizadas sínteses com diferentes tempos de cristalização. Os produtos de reação foram caracterizados por difração de raios X, espectroscopia na região do infravermelho, análise termogravimétrica, análise térmica diferencial, microscopia eletrônica de varredura e adsorção de nitrogênio para cálculo de área específica pelo método BET. A amostra que apresentou maior proporção de zeólita NaA foi utilizada como adsorvente em soluções de Cu2+, Ni2+ e Cd2+ com concentrações iniciais de 25 a 400 mg/L. A concentração de equilíbrio desses metais, após remoção pela zeólita NaA, foi determinada por espectrofotometria de absorção atômica. Os resultados mostraram que o aumento da alcalinidade e do tempo de cristalização favoreceu a obtenção de sodalita, uma fase zeolítica concorrente à Zeólita A, nos produtos de síntese. A zeólita NaA provou ser um excelente adsorvente para remoção dos metais analisados, apresentando uma capacidade de adsorção máxima de aproximadamente 79, 65 e 32 mg/g para Cd2+, Cu2+ e Ni2+, respectivamente. O modelo de isoterma de adsorção que melhor descreveu a remoção de metais pela zeólita NaA foi o de Langmuir. / The aim of this work was to study the synthesis of zeolite NaA under hydrothermal conditions and use it as adsorbent of heavy metals. To synthesize zeolite NaA, kaolin from the city of Ipixuna, Pará, was calcined at 700 °C for 3 hours and used as source of silica and alumina. For comparison purposes, aluminum chloride and sodium metasilicate were also used in the synthesis of zeolites as precursors of Si and Al. The influence of alkalinity on the synthesis of the zeolitic products was evaluated using different NaOH concentrations. All the syntheses were performed at 110 °C by autoclaving. To understand the influence of time on the type and relative amount of the obtained phases, syntheses with different crystallization times were carried out. The reaction products were characterized by means of X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, thermal differential analysis, scanning electron microscopy and nitrogen adsorption for calculating surface area by the BET method. One of the samples, which exhibited the highest content of zeolite NaA, was used as adsorbent of Cu2+, Ni2+ and Cd2+ solutions with initial concentrations ranging from 25 to 400 mg/L. The equilibrium concentration of these heavy metals, after removal by zeolite NaA, was determined by atomic absorption spectrophotometry. The results showed that increasing alkalinity of the reaction medium led to the formation of sodalite, a concurrent zeolitic phase, in the products. Zeolite NaA turned out to be an excellent adsorbent for removing heavy metals, with an adsorption capacity of 79, 65 and 32 mg/g for Cu2+, Cd2+ and Ni2+, respectively. The Langmuir isotherm model was the most appropriate to describe the removal of metals by zeolite A.

Mesoporous silica has shown great potential as an adsorbent for environmental contaminants and as a host for imaging and therapeutic agents. Mesoporous silica materials have a high surface area, tunable pore sizes and well defined surface properties which are governed by the surface hydroxyl groups. Surface modification of the mesoporous silica can tailor the adsorption properties for a specific metal ion or a small drug molecule by providing better sites for chelation or electrostatic interactions. Iron oxide / mesoporous silica core shell materials couple the favorable properties of both the iron oxide and mesoporous silica materials. The core-shell materials have higher adsorption properties compared to the parent material. With magnetic iron oxide nanoparticle cores, an additional magnetic property is introduced that can be used as magnetic recovery or separation. Heavy metals such as Chromium (Cr) and Arsenic (As) discharged from residential and environmental sources pose a serious threat to human health as well as groundwater pollution. In this thesis, iron oxide nanoparticles and nanofibers were coated with mesoporous silica and functionalized with (3-aminopropyl)triethoxysilane (APTES) using the post synthesis grafting method. The parent and the functionalized magnetic silica samples were characterized using powder X-ray diffraction (pXRD), thermal gravimetric analysis (TGA), Fourier Transform Infrared (FTIR) spectroscopy and nitrogen adsorption desorption isotherms for surface area and pore volumes. These materials were evaluated for Cr(III) and As(III)/As(V) adsorption from aqueous solutions in the optimum pH range for the specific metal. The aminopropyl functionalized magnetic mesoporous silica displayed the highest adsorption capacity for Cr(III) and Cu(II) of all the materials evaluated in this study. The high heavy metal adsorption capacity was attributed to a synergistic effect of iron oxide nanoparticles and amine functionalization on mesoporous silica as well as a judicious choice of pH. Modified magnetic mesoporous silica material was also found to have high adsorption capacity for high and low pH aqueous solutions of Uranium (VI). Tuning the loading and release of a small drug molecule (5-FU) onto these iron oxide/ mesoporous silica core-shell materials was also investigated. The polarity of the solvent used to load 5-FU onto the host had an impact not only on the loading but also on the release percentage of 5-FU. The synthesis of a novel core-shell material with a hematite nanofiber core and a SBA type mesoporous silica shell was also explored.

No description available.

Urban runoff is generated by precipitation of rain and snowmelt on impervious surfaces.  The increasing demand of urbanization causes contaminants to accumulate on roads,  roofs and pathways. In turn, as runoff wash off these surfaces, contaminants such as heavy metals, particles and organic pollutants end up in the stormwater. Urban stormwater ponds improve water quality of runoff by facilitating contaminants in form of particles. To preserve the function of a stormwater pond accumulated sediment must periodically be removed.Therefore, upland disposal alternatives should be evaluated. This study examined stormwater sediment and outlet stormwater quality in seven and four ponds respectively in the vicinity of Halmstad. 7 heavy metals and 24 organic contaminants were analysed in both sediments and stormwater. Results showed metal and organic contaminant concentrations in stormwater pond discharge and sediment exceeding concentrations reported in guideline values. From the analysed heavy metals, Zn and Pb was considered the most critical contaminants. Heavier organic compounds were more frequently quantified than lighter ones, where 42 % of the analysed organic contaminants were quantified in at least one sample. Variability between inlets and outlets, between ponds and between sampling occasions was observed. The observed variability suggests that the contamination level is influenced by catchment area characteristics and activities. Significant correlation from Spearman’s rank correlation was found between the individual heavy metals (Cu, Cr, Ni, Pb and Zn), which suggest they originate from similar sources

Association constants for the formation of lead (II) chloride complexes were studies in aqueous solutions also containing copper (II) and cadmium (II) ions. The ionic strength was adjusted with sodium perchlorate to resemble that of sea water. The temperature was set at fixed values between 5° and 35° C to determine the effect on the equilibria in these systems. The total metal concentration was less than 10-8 M. Differential pulse anodic striping voltammetry was used with a conventional three electrode system and a thin-film working electrode of Pt/Hg. Complex formation was followed as a function of the ligand concentration by observing the shift in the stripping peak potential Ep. The measured Ep and temperature data were used to obtain thermodynamic information on the formation of the complex ions. The activity coefficients were assumed constant at a given temperature. The values for the base ten logarithm of the overall formation constants at 25.0° are 1.11, 1.48 and 1.83 for PbCl+, PbCl°2 and PbCl-3 complexes respectively. These results are in good agreement with literature values. The Δ H of formation values for those complexes in solution were found to be positive. Tentative results were obtained for copper (II) which was only weakly complexed with Cl - under the present conditions.

This master‘s thesis concerns with occurrence of heavy metals in the environment, mainly in the matrices of bioindicators. Special attention is given to occurrence of mercury in the environment and its quantification in bioindicators. Mercury and its compounds are today considered as one of the most significant contaminants in the environment. Some sorts of mushrooms cumulate sizable amounts of mercury in their fruiting body and therefore we can use them to consider loading of different areas. Eight areas in Vizovice and its surroundings were chosen for these purposes and during the years 2006 – 2008 harvested 50 samples from 19 sorts of mushrooms from there. The concentrations of Hg were determined in all samples by single-purpose absorption spectrometer AMA 254. Comparison of the mercury content between individual sorts of mushrooms in the same area as well as comparison of loading of areas was performed and also bioaccumulation ability of individual sorts of mushrooms was determined.

Today is the food quality a discussed topic not only in the Czech Republic. In this work we focused on micronutrients and heavy metals in strawberries. Strawberries are very attractive fruit consumed by all age groups from children to seniors. These bring not only gustatory pleasure but also positive effects on human organism. Soft fruit structure could contribute to the accumulation of heavy metals, which can be dangerous in certain quantities in terms of acute toxicity or what is more likely in terms of chronic exposure. In the spring - autumn of 2011 samples from the home cultivation of strawberries in the Czech Republic were collected and also samples of fruits that are commonly available in supermarket chains in this period were purchased. The element analysis was performed by the mass spectrometry with inductively coupled plasma, which belongs to a very sensitive method of elements determination.