RESUMO AVALIAÇÃO DA BIODISPONIBILIDADE DE METAIS PESADOS APÓS VERMICOMPOSTAGEM EM PRESENÇA DE LIXO ELETRÔNICO Os metais pesados presentes no lixo eletrônico, descartado de forma inadequada, podem se tornar biodisponíveis após a vermicompostagem, representando risco ao ambiente. Foram realizados experimentos de vermicompostagem em pequena escala na presença de placas de circuito impresso (PCI) para investigar a migração de metais pesados (Cu, Pb, Zn, Ni e Sn) para o composto obtido, assim como a mobilidade e biodisponibilidade desses metais. Os resultados evidenciaram elevados teores totais de Pb, Sn e Cu nas amostras de esterco com resíduo eletrônico (ERE) e vegetais com resíduo eletrônico (VRE). Levando-se em consideração os teores iniciais dos metais nas PCIs e as concentrações dos mesmos no composto obtido, a ordem de migração desses metais para as amostras ERE e VRE foi Sn (23,1 %)>Pb (18,4 %)>Ni (4,63 %)>Zn (0,46 %)>Cu (0,14 %) e Sn (24,3 %)>Pb (23,6 %)>Ni (11,33 %)>Zn (1,76 %)>Cu (0,60 %), respectivamente. A avaliação da mobilidade e biodisponibilidade dos metais no composto foi realizada mediante a extração sequencial em três etapas, sendo F1 a fração trocável, F2 a fração orgânica e F3 a fração residual. O fator de biodisponibilidade (FB) foi obtido pela razão entre a soma das frações F1 e F2 pela soma total das frações (F1 + F2 + F3). O maior valor do FB (0,92) foi encontrado para o Pb, metal pesado considerado de maior preocupação ambiental neste estudo, o que indica alta mobilidade desse metal, podendo tornar-se biodisponível.

ABSTRACT Heavy metals contained in electronic waste, if discarded improperly, can become bioavailable after vermicomposting, posing a risk to the environment. Small-scale vermicomposting experiments were carried out with printed circuit boards (PCBs) to investigate the migration of heavy metals (Cu, Pb, Zn, Ni, and Sn) to the final compost, as well as the mobility and bioavailability of these metals. High total levels of Pb, Sn and Cu in samples of manure with electronic waste (MEW) and vegetables with electronic waste (VEW) were detected. Based on the initial metal levels in the PCBs and their concentration in the resulting compost, the order of migration of these metals to the MEW and VEW samples was Sn (23.1 %)>Pb (18.4 %)>Ni (4.63 %)>Zn (0.46 %)>Cu (0.14 %) and Sn (24.3 %)>Pb (23.6 %)>Ni (11.33 %)>Zn (1.76 %)>Cu (0.60 %), respectively. Mobility and bioavailability of these metals in the compost were evaluated by three-stage sequential extraction, where F1 was the exchangeable fraction, F2 the organic fraction and F3 the residual fraction. The bioavailability factor (BF) was calculated by the ratio of the sum of fractions F1 and F2 divided by the total sum of the fractions (F1 + F2 + F3). The highest bioavailability factor (BF = 0.92) was found for Pb, the heavy metal considered the greatest environmental concern in this study, indicating the high mobility and the possibility of becoming bioavailable of this metal.

In this work, hydrotalcite, a layered double hydroxide, had its ion exchange properties combined with the magnetic properties of iron oxide to produce a magnetic adsorbent, HT-Fe 500. These magnetic composites can be used as adsorbents for anionic contaminants in water and subsequently removed from the medium by a simple magnetic process. Removal of chromium (VI) from aqueous solutions using HT-Fe 500 was achieved using batch adsorption experiments. The adsorption capacity, calculated with the Langmuir-Freundlich model showed to be dependent on temperature, reaching values of 25.93 and 48.31 mg g-1, respectively, for temperatures of 25 and 30 ºC.

In this work, hydrotalcite, a layered double hydroxide, had its adsorption and ion exchange properties combined with the magnetic properties of iron oxide to produce a magnetic adsorbent, HT-Fe. The removal of As(V) by a HT-Fe adsorbent was evaluated under various conditions. The Kinetic process was well described by a pseudo-second order rate model. The maximum adsorption capacity, calculated with the Langmuir model showed to be dependent on pH, reaching values of 24.09, 10.19 and 7.44 mg g-1, respectively, for pH values of 4.0, 7.0 and 9.0. The inhibition by competition of anions is dependent on the type of ionic species.

A determinação de As por espectrometria de absorção atômica com geração de hidretos (HG-AAS) constitui um método simples, sensível, preciso e de baixo custo. Entretanto, essa técnica requer a pré-redução das espécies de As(V), o que se obtém através do uso de agentes redutores como o KI. Em extratos contendo agentes oxidantes, a pré-redução do As é comprometida, como acontece em extratos obtidos pela aplicação do método BCR (acrônimo francês para Community Bureau of Reference) para a extração sequencial de As em sedimentos. O objetivo deste trabalho foi avaliar as condições de redução do As(V) a As(III), de modo a permitir o uso da HG-AAS para a quantificação do arsênio em extratos obtidos a partir do método BCR. Foram avaliadas condições reacionais utilizando KI, L-cisteína e ácido ascórbico. Para cada uma das etapas de extração do método BCR, diferentes condições de pré-redução possibilitaram a detecção quantitativa do As presente. O uso do método BCR para a extração de arsênio em amostras de sedimentos contaminadas e a aplicação das condições de pré-redução do As(V) selecionadas, seguida pela detecção por HG-AAS, forneceram percentagens de recuperação entre 91 e 99 %.

The determination of As by hydride generation atomic absorption spectroscopy (HG-AAS) is a simple, sensitive, precise and low-cost method. However, this technique requires the pre-reduction of the existing As(V) species, which is obtained by the use of reducing agents such as KI. In extracts containing oxidizing agents, the pre-reduction of As is impaired, as it occurs in extracts obtained by the BCR (French acronym for Community Bureau of Reference) method for the sequential extraction of As in sediments. The objective of this study was to evaluate the conditions for the reduction of As(V) to As(III) in a way that allows the use of HG-AAS for the quantification of arsenic in extracts obtained using the BCR method. Reaction conditions were evaluated using KI, L-Cysteine and ascorbic acid. For each of the BCR extraction steps, different conditions of pre-reduction enabled the quantitative detection of As. The use of the BCR method for the extraction of arsenic from contaminated sediment samples and the application of pre-reduction conditions of the As(V) followed by HG-AAS detection resulted in relative recoveries between 91 and 99 %.

The oxidation of arsenic (As(III) to As(V)) in water samples was performed by heterogeneous photocatalysis using a TiO2 film immobilized inside a photochemical reactor. After oxidation, As(V) was removed from the water samples by coprecipitation with ferric sulfate. The final conditions of oxidation and arsenic removal (TiO2 film prepared with a suspension: 10% (w/v); pH: 7.0; oxidation time: 30 min and Fe3+ concentration: 50 mg L-1) were applied in natural water samples which were supplemented with 1.0 mg L-1 of As(III) to verify the influence of the matrix. After treatment, more than 99% of arsenic was removed from the water.

This article deals with synthesis and reactivity of complexes with triphenylstibine (SbPh3) as the ligand. A comparative study of analogous complexes of triphenylphosphine (PPh3) and triphenylarsine (AsPh3) with platinum in the oxidation states zero, two and four is included. The bibliographic revision includes publications since 1936, when the first Pt(II) complex with triphenylstibine was described.

Objetivo. Determinar os teores de selênio em alimentos consumidos no Brasil. Métodos. O trabalho foi desenvolvido de 1993 a 1999. As amostras de alimentos foram coletadas no comércio varejista em vários estados do Brasil. Os teores de selênio foram determinados por meio de espectrofotometria de absorção atômica, utilizando-se a técnica de geração de hidretos, e oxidação da matéria orgânica por via úmida. Resultados. Os teores mais elevados de selênio foram encontrados nos produtos de origem animal, sobretudo nos pescados, e nos produtos derivados do trigo. Observou-se que os teores de selênio nos alimentos de origem vegetal foram, de modo geral, inferiores a 5,0 µg/100g. Conclusões. No Brasil, a presença de pescados, principalmente, e de outros produtos de origem animal é importante na dieta para garantir o consumo dos teores recomendados de selênio.

Objective. To determine the selenium content of foods consumed in Brazil. Methods. The project was carried out between 1993 and 1999. The food samples were collected in stores in several Brazilian states. The levels of selenium were determined by hydride generation atomic absorption spectrophotometry and by wet oxidation. Results. The highest levels of selenium were found in animal products, especially fish, and in wheat products. We found that plant products generally had selenium levels of less than 5.0 µg/100 g. Conclusions. In Brazil a diet rich in animal products, especially fish, is important in ensuring consumption of the recommended levels of selenium.

Amostras de ácidos húmicos de origem comercial (Fluka AG) foram usadas na avaliação do comportamento de adsorção de íons Cu2+. O modelo matemático descrito pela equação de adsorção de Langmuir em sua forma linear foi aplicado, obtendo-se os valores da capacidade máxima de adsorção b e da constante relacionada à energia de ligação a. Alíquotas de soluções de nitrato de cobre contendo várias concentrações desse metal foram adicionadas às amostras de suspensões de ácidos húmicos a pH constante. As isotermas apresentaram duas regiões distintas de adsorção, tanto a pH 4 como a pH 5, mostrando que o fenômeno adsortivo ocorre em duas etapas distintas, de acordo com o tipo de interação entre os ácidos húmicos e o cobre. As amostras de ácidos húmicos mostraram maior capacidade máxima de adsorção ao pH 5 do que ao pH 4, enquanto que a constante relacionada à energia de ligação foi maior em pH 4.

Commercial samples of humic acids (Fluka AG) were used to evaluate the adsorption behaviour of Cu2+ ions. The mathematical model described by Langmuir's adsorption equation was applied and the values of the maximum adsorption capacity b and those of the constant related to the bonding energy a were obtained. Aliquots of copper nitrate solutions with different copper concentrations were added to the humic acid suspensions at constant pH values (4.0 and 5.0). The Langmuir isotherms presented two distinct adsorption regions, showing that the adsorptive phenomenon occurs in two distinct steps according to the copper-humic site interaction. Samples of humic acids showed higher maximum adsorption capacity at pH 5 than at pH 4, while the constant a related to bonding energy was higher at pH 4.

The chemical and physical characterization of coastal peat has been studied. It was examined the pH, organic matter content and elementary and XRD analyses, among other characteristics. The peat was then applied to the retention and competition of metal micronutrients (Cu and Zn) from metal nitrate solutions. The retention was affected by both the pH and time of adsorption, while the competitive character of these metals for the substrate was relevant to each pH examined.

In environmental studies it is necessary to know the adsorption behavior of metals by soils, since the unfavorable effects of heavy metals and even the micronutrients at high concentrations in the environment are related to these adsorbents' ability to immobilize them. A sample of a humic yellow red oxisol from Araponga region in the State of Minas Gerais, Brazil, was used to verify the adsorption behavior of Cu2+ ions in this substrate. The mathematical model described by Langmuir's adsorption equation in its linearized form was applied and the values of the maximum capacity b and those of the constant related to the bonding energy a were obtained. Aliquots of copper nitrate solutions containing several concentrations of this metal were added to soil samples, the pH being predetermined for developing the adsorption experiments. The chemical and physical characterization of soil sample were performed by determining the organic carbon, nitrogen and phosphorus concentrations, cation exchange capacity (CEC), pH, concentration of metals (Al, Fe, K, Mg, Ca, Zn, Cu, Ni, Cr, Co, Pb, and Cd), granulometric analysis and X-ray diffraction. Langmuir isotherms presented two distinct adsorption regions at both pH 4 and pH 5, showing that the adsorptive phenomenon occurs in two distinct stages. The adsorption sites for the lower part presented greater bonding energy and low adsorption capacity compared with the adsorption sites of the part of the curve corresponding to higher Cu concentrations in the equilibrating solution.

The physical and chemical characterization of vermicompost from bovine manure has been studied. It was examined the pH and cation exchangeable capacity (CEC), organic matter content, electric conductivity and elementary and XRD analyses, among other characteristics. The vermicompost was then applied to the retention and competition of metal micronutrients and pollutants (Cu and Zn) from metal nitrate solutions. The retention was affected by both the pH and adsorption time, while the competitive character of these metals for the substrate was relevant to each pH examined.