Avaliação ecotoxicológica de metais/metalóides e interferentes endócrinos em frações de substâncias húmicas de diferentes tamanhos moleculares

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ocorrências e distribuição de bactérias resistentes a metais pesados em sedimentos da Baía do Araça, São Sebastião (SP)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Metagenoma de comunidades microbianas expostas à radiação natural e a metais

Many species have specialized to live in the most varied existing environments showing the remarkable adaptability of the microbial world the most diverse physicochemical conditions. Environments exposed to natural radiation and metals are scarce around the world, presenting a microbiota still unknown. With a total number estimated between 4 and 6 x 1030 microrganisms on earth, they constitute an enormous biological and genetic pool to be explored. Metagenomic approach independent of cultivation, provides a new form to access to the potential genomic environmental samples becoming a powerful tool for the elucidation of ecological functions, metabolic profiles, as well as to identify new biomolecules. In this context, the genetic material of environmental soil and water samples from Açude Boqueirao Parelhas-RN, under the influence of natural radiation and the presence of metals, was extracted, pirosequencing and the generated sequences were analyzed by bioinformatics programs (MG-RAST and STAMP). Taxonomic comparative profiles of both samples showed high abundance of Domain Bacteria, followed by a small portion attributable to Eucaryota Domains, Archaea and Viruses. Proteobacteria, Actinobacteria and Bacterioidetes phyla showed the greater dominance in both samples. Important genera and species associated with resistance to various stressors found in region were observed. Sequences related to oxidative and heat stress, DNA replication and repair, and resistance to toxic compounds were observed, suggesting a significant relationship between the microbiota and their metabolic profile, influenced by regional environmental variables. The results of this study add valuable and unpublished data on the composition of microbial communities in these regions

Aplicação da tecnologia eletroquímica para a remoção e monitoramento de metais pesados em efluentes aquosos

Heavy metals are present in industrial waste. These metals can generate a large environmental impact contaminating water, soil and plants. The chemical action of heavy metals has attracted environmental interest. In this context, this study aimed to test t he performance of electrochemical technologies for removing and quantifying heavy metals. First ly , the electroanalytical technique of stripping voltammetry with glassy carbon electrode (GC) was standardized in order to use this method for the quantificatio n of metals during their removal by electrocoagulation process (EC). A nalytical curves were evaluated to obtain reliability of the determin ation and quantification of Cd 2+ and Pb 2+ separately or in a mixture. Meanwhile , EC process was developed using an el ectrochemical cell in a continuous flow (EFC) for removing Pb 2+ and Cd 2+ . The se experiments were performed using Al parallel plates with 10 cm of diameter (  63.5 cm 2 ) . The optimization of conditions for removing Pb 2+ and Cd 2+ , dissolved in 2 L of solution at 151 L h - 1 , were studied by applying different values of current for 30 min. Cd 2+ and Pb 2+ concentrations were monitored during electrolysis using stripping voltammetry. The results showed that the removal of Pb 2 + was effective when the EC pro cess is used, obtaining removals of 98% in 30 min. This behavior is dependent on the applied current, which implies an increase in power consumption. From the results also verified that the stripping voltammetry technique is quite reliable deter mining Pb 2+ concentration , when compared with the measurements obtained by atomic absorption method (AA). In view of this, t he second objective of this study was to evaluate the removal of Cd 2+ and Pb 2+ (mixture solution) by EC . Removal efficiency increasing current was confirmed when 93% and 100% of Cd 2+ and Pb 2+ was removed after 30 min . The increase in the current promotes the oxidation of sacrificial electrodes, and consequently increased amount of coagulant, which influences the removal of heavy metals in solution. Adsortive voltammetry is a fast, reliable, economical and simple way to determine Cd 2+ and Pb 2+ during their removal. I t is more economical than those normally used, which require the use of toxic and expensive reagents. Our results demonstrated the potential use of electroanalytical techniques to monitor the course of environmental interventions. Thus, the application of the two techniques associated can be a reliable way to monitor environmental impacts due to the pollution of aquatic ecosystems by heavy metals.

Distribuição dos metais nas poeiras colhidas em Estarreja: estudo da mobilidade e impacto potencial dos metais no ambiente

As poeiras urbanas, vulgarmente designadas na literatura por street dusts ou road dusts, são misturas heterogêneas de partículas minerais do solo e partículas resultantes do tráfego, formando um material com características únicas e específicas de cada local. Estas partículas, geralmente enriquecidas com elementos potencialmente tóxicos, quando inaladas ou ingeridas poderão ser um risco para a saúde das populações. Neste trabalho foram recolhidas 21 amostras de poeiras urbanas na cidade de Estarreja assim como amostras representativas de partículas relacionados com o tráfego (poeiras resultante do desgaste dos travões e das marcações dos pavimentos e estradas) com o objetivo de investigar a contribuição relativa destas partículas no comportamento geoquímico dessas amostras e o risco associado para as populações locais. Para a concretização do objetivo proposto caracterizou-se química e mineralogicamente as amostras de poeiras urbanas e as partículas relacionadas com o tráfego e avaliou-se a disponibilidade e bioacessibilidade para três elementos considerados potencialmente tóxicos (Cu, Pb e Zn) usando uma combinação de ensaios: (a) digestão ácida; (b) extração sequencial para identificar o fracionamento do Cu, Pb e Zn nas diferentes fases-suporte dos metais, e (c) bioaccessibilidade oral in vitro. Os resultados da análise química mostram que as poeiras dos travões apresentam concentrações elevadas em Fe, Cu, Zn, Mn, Ba, Sb, Cr e Ni sendo de referir diferenças composicionais significativas entre as amostras estudadas. A amostra de tinta contém teores elevados de Ba, Ca, Ti e Pb e também pode conter outros elementos tais como Co, Cr, Cu, Mn. Mineralogicamente constata-se que as amostras de poeiras dos travões tem uma composição mineralógica semelhante mostrando que são constituídas por uma elevada percentagem de material de baixa cristalinidade, grafite e óxidos/hidróxidos de Fe amorfos. A amostra de tinta de marcação dos pavimentos das estradas é composta por material mais cristalino do que a poeira dos travões e é essencialmente constituída por carbonatos (maioritariamente dolomite) e também por barite (em menor quantidade). Os resultados obtidos nas amostras de poeiras urbanas indicam a existência de associações de elementos que definem claramente a componente geogénica e/ou antropogénica e apontam para diferenças entre essas associações nas duas frações estudadas (250 m e 63 m). A heterogeneidade das poeiras é revelada pela existência de partículas com origem geogénica (por exemplo quartzo e aluminossilicatos), de partículas com características marcadamente antropogénicas (partículas enriquecidas em Fe, Pb, Zn e Cu) ou ainda de partículas com origem mista (óxidos de Fe e Ti). Os resultados da extração química seletiva sequencial permitiu concluir que, nas amostras em estudo, as fases de troca e ácido-solúveis são as fases suporte mais importantes para o Cu, Pb e Zn Os resultados dos ensaios de bioacessibilidade mostraram também que uma percentagem significativa de Cu, Pb e Zn total está disponível para absorção gástrica. Este estudo destaca também a necessidade de se caracterizar em detalhe as propriedades intrínsecas das partículas antrópicas presentes nas poeiras urbanas, de forma a compreender as variações da fração bioacessível nos diferentes elementos estudados assim como nas diferentes frações.

Avaliação da correlação entre os parâmetros, carbono orgânico total e elementos tóxicos, em solo de um posto de serviço e revenda de combustíveis

Today a major responsibility for the contamination of soil and groundwater and surface water are establishments known as gas stations of fuel which has attracted increasing attention from both the general population as the state agencies of environmental control due to leaks in storage tanks and mainly to disruption of pipe corrosion of tanks and pumping. Other services, like oil changes and car wash are also causes for concern in this type of establishment. These leaks can cause or waste produced, and the contamination of aquifers, serious health problems and public safety, since most of these stations located in urban areas. Based on this, the work was to evaluate soil contamination of a particular service station and fuel sales in the city of Natal, through the quantification of heavy metals like Cd, Cu, Cr, Ni, Pb, Zn of total organic carbon (TOC) and organic matter using different techniques such as optical emission spectrometry with inductively coupled plasma source (ICP OES), Total Organic Carbon analyzer and gravimetric analysis respectively. And also to characterize the soil through particle size analysis. Samples were taken in 21 georeferenced points and collected in the same period. The soils sampled in sampling stations P3, P5, P6, P10, P11, P12, P13, P14, P15, P17, P18 and P20 showed the smallest size fractions ranging from fine sand to medium sand. The other study sites ranged from fine sand to medium sand, except the point P8 showed that only the type size medium sand and P19, indicating a particle size of the coarse type. The small correlation of organic matter with the elements studied in this work suggests that these are not of anthropogenic origin but geochemical support

Remoção de metais pesados de soluções usando um biopolímero

Comunicação seleccionada e artigo em Livro de Actas

O estado da arte da cromatografia associada à espectrometria de massas acoplada à espectrometria de massas na análise de compostos tóxicos em alimentos

Chromatography combined with several different detection systems is one of the more used and better performing analytical tools. Chromatography with tandem mass spectrometric detection gives highly selective and sensitive analyses and permits obtaining structural information about the analites and about their molar masses. Due to these characteristics, this analytical technique is very efficient when used to detect substances at trace levels in complex matrices. In this paper we review instrumental and technical aspects of chromatography-tandem mass spectrometry and the state of the art of the technique as it is applied to analysis of toxic substances in food.

Desempenho analítico de laboratórios prestadores de serviço na determinação de metais em águas

Analytical laboratories are expected to produce reliable results. Decision makers are guided in their actions (financial, legal and environmental) using analytical data provided by numerous laboratories. This work aimed to evaluate the analytical performance of Brazilian laboratories on producing trustworthy results. Nineteen laboratories, accredited and non-accredited ones, were contracted to analyze a USGS (United States Geological Survey) certified water sample for 17 chemical elements (mostly metals) without knowing the origin of the sample. Considering all the results produced, only 35% of them were valid. Three laboratories present satisfactory performances, whereas the majority showed a very poor overall performance. The outcomes of this work show the need for a more effective analytical quality program to Brazilian laboratories.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Sulfetos volatilizáveis por acidificação e metais extraídos simultaneamente na avaliação de sedimentos de água doce

This paper discusses the historical and methodological fundaments of the dynamics and quantification of acid volatile sulfides (AVS) and simultaneously extracted metals (SEM) in aquatic sediments. It also discusses the SEM/AVS relationship, which involves several controversial aspects such as sulfide stability, sulfide-organic matter interaction, and the inability to predict the toxicity of organic compounds in the environment. This relationship is an important tool for the inference of metal bioavailability. The use of ecotoxicological tests with target organisms regulated by international standards is also a relevant aspect.

Avaliação de metais traços e íons majoritários em águas de chuva na cidade de São Paulo

Rainfall samples collected in the downtown area of São Paulo city, during 2003, exhibited average concentrations of cadmium, lead and copper of 1.33, 8.52 and 49.5 nmol L-1, respectively. Among the major ions, NH4+ was the predominant species followed by NO3-, SO4(2-) and Ca2+, with volume weighed mean (VWM) concentrations of 37.1, 20.1, 11.9 and 10.8 µmol L-1, respectively. All the determined species showed high inter-events variability, including free H+ ions whose VWM concentration was 4.03 µmol L-1, corresponding to a pH value of 5.39.

Extração seletiva de metais pesados em sedimentos de fundo do Rio Tietê, São Paulo

Sediment samples from Tietê river were submitted to chemical and sequential extractions of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn). It was followed a single extraction by using 0.1 mol L-1 hydrochloric acid and a sequential procedure to evaluate possible chemical associations described as exchangeable, carbonate, reducible oxides, sulfide, organic matter and residual fractions. High concentrations of heavy metals were determined at Pirapora reservoir, which is closer to the Metropolitan Area of São Paulo while for Barra Bonita reservoir, the results showed low concentrations for such elements. Acid volatile sulfides, grain size distribution and carbon contents were also determined.

Estudo da mobilização de metais e elementos traços em ambientes aquáticos do semi-árido brasileiro aplicando análises de componentes principais

The spatial and temporal retention of metals has been studied in water and sediments of the Gavião River, Anagé and Tremedal Reservoirs, located in the semi-arid region, Bahia - Brazil, in order to identify trends in the fluxes of metals from the sediments to the water column. The determination of metals was made by ICP OES and ET AAS. The application of statistical methods showed that this aquatic system presents suitable conditions to move Cd2+ and Pb2+ from the water column to the sediment.

Disponibilidade de metais pesados em Latossolo com aplicação superficial de escória, lama cal, lodos de esgoto e calcário

O objetivo deste trabalho foi avaliar alguns atributos químicos do solo e a disponibilidade de cádmio (Cd), cromo (Cr), níquel (Ni), mercúrio (Hg), chumbo (Pb) e arsênio (As), por meio da extração pelo DTPA,em conseqüência da aplicação superficial de escória de aciaria, lama cal e lodos de esgoto centrifugados e de biodigestores, nas doses 0 (testemunha), 2, 4 e 8 Mg ha-1 e um tratamento adicional composto pela calagem superficial na dose 2 Mg ha-1. O experimento foi conduzido em delineamento de blocos ao acaso, em condições de campo, em área sob sistema plantio direto, durante 2003 e 2004. A aplicação superficial de escória de aciaria,lama cal, lodo de esgoto centrifugado e de biodigestor, até a dose 8 Mg ha-1, assim como o calcário na dose 2 Mg ha-1, não trazem problemas de disponibilidade ao ambiente, com relação aos metais pesados Cd, Cr, Hg, Pb, Ni e As, quando aplicados sobre a superfície em Latossolo Vermelho distrófico, no sistema plantio direto. A fitodisponibilidade de metais pesados às culturas da soja e aveia-preta foi nula, quando foram aplicadas doses de até 8 Mg ha-1 de lodo de esgoto, escória e lama cal sobre a superfície do solo, no sistema plantio direto