Heavy metal concentrations in soils from a remote oceanic island, Fernando de Noronha, Brazil

This paper examines the role of parent rock, pedogenetic processes and airborne pollution in heavy metal accumulation in soils from a remote oceanic island, Fernando de Noronha, Brazil. We studied five soil profiles developed from different volcanic rocks. Mineralogical composition and total concentrations of major and trace elements were determined in 43 samples. The obtained concentrations range for heavy metals were: Co: 26-261 ppm; Cu: 35-97 ppm; Cr: 350-1446 ppm; Ni: 114-691 ppm; Zn: 101-374 ppm; Hg: 2-150 ppb. The composition of soils is strongly affected by the geochemical character of the parent rock. Pedogenesis appears to be responsible for the accumulation of Zn, Co, and, to a lesser extent, of Ni and Cu, in the upper, Mn- and organic carbon-enriched horizons of the soil profiles. Pedogenic influence may also explain the relationship observed between Cr and the Fe. Hg is likely to have been added to the soil profile by long-range atmospheric transport. Its accumulation in the topsoil was further favoured by the formation of stable complexes with organic matter. Clay minerals do not appear to play an important role in the fixation of heavy metals.

Métodos para fabricação de microeletrodos visando a detecção em microambientes

Analysis at microenvironments, like single cells or in minute volumes (nL), is an area of great interest for analytical and biological sciences. Measurements at these experimental conditions demand analytical tools (microelectrodes) capable of monitoring with rapid response, good resolution and minimal perturbation of the system. The major drawbacks in producing these microscopic electrodes have been largely overcome, principally due to the development of new fabrication methods. In this review, these procedures are described with emphasis to those devoted to the construction of microelectrodes for application in microenvironments. Examples of our efforts to use these devices as effective electrochemical sensors are also addressed.

Mercúrio total em cabelo de crianças de uma população costeira, Cananéia, São Paulo, Brasil

Os níveis de mercúrio (Hg) total em cabelos estão diretamente relacionados à alimentação, particularmente ao consumo de peixes por populações costeiras com grande representação caiçara. No presente estudo foram avaliados os níveis de mercúrio total em cabelos de crianças com idade entre 4 e 12 anos, pertencente a três escolas públicas da cidade de Cananéia, São Paulo, Brasil. Os resultados obtidos (mediana e intervalo) para mercúrio total foram de: 0,04mg.kg-1 (0,01-0,77mg.kg-1), 0,39mg.kg-1 (< 0,01-3,33mg.kg-1) e 0,39mg.kg-1 (< 0,01-2,81mg.kg-1) considerando as escolas ES1, ES2 e ES3, respectivamente. Em geral, os valores encontrados estiveram bem abaixo do valor preconizado pela Organização Mundial da Saúde para uma população adulta não exposta ao mercúrio (2,0mg.kg-1). Os baixos valores observados e a inexistência de valores de referência para mercúrio total em cabelos de crianças brasileiras possibilitam a consideração desses valores como possível referência nacional em cabelos de populações costeiras, uma vez que foram obtidos em região de baixo impacto ambiental.

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

Toxic and essential elements in blood from delivering women in selected areas of Sao Paulo State, Brazil

This study was designed to evaluate the degree of environmental contamination and possible exposure of pregnant women to toxic elements in seven selected areas of Sao Paulo State, Brazil. The overall median concentration of Mo in maternal blood was 0.53 mu g L(-1), highly significant differences found between sites (p < 0.0001). Cd was found to be low overall - 0.09 mu g L(-1) (0.01-0.58 mu g L(-1)) - with mothers from the Coastal and Rural 1 sites having the highest levels (p < 0.016). Median Hg concentration was 0.60 mu g L (1) (0.06 mu g L (1)-4.35 mu g L (1)); median Pb level was 16.2 mu g L (1) (3.5-57.7 mu g L(-1)) and no differences between sites were observed for both metals. Median Mn level was 16.7 mu g L(-1) (7.0-39.7 mu g L(-1)), being highest in Urban 2 site (p < 0.016). Concentrations of maternal Co were found to range between 0.06 mu g L(-1) and 1.1 mu g L(-1) (median 0.25 mu g L(-1)) and As level was 0.60 mu g L(-1) (0.10-3.8 mu g L(-1)) overall, with no statistical significance between sites for Co and As. Median Se concentrations were found to be 64 mg L(-1) (36-233 mu g L(-1)), with the highest median levels found in Urban 3 site; site differences were statistically significant (p < 0.0001). Correlation for each element (between paired maternal and cord blood) was measured only in Rural site 1; significant correlation was shown for Hg, Pb, Mn and Co (p < 0.05). These findings may be interpreted as indicating low environmental contamination in Sao Paulo State, Brazil. These findings could also indicate that pregnant women have little or no contact with pollutants, possibly due to awareness campaigns carried out by public health practitioners.

Density functional theory investigation of 3d, 4d, and 5d 13-atom metal clusters

The knowledge of the atomic structure of clusters composed by few atoms is a basic prerequisite to obtain insights into the mechanisms that determine their chemical and physical properties as a function of diameter, shape, surface termination, as well as to understand the mechanism of bulk formation. Due to the wide use of metal systems in our modern life, the accurate determination of the properties of 3d, 4d, and 5d metal clusters poses a huge problem for nanoscience. In this work, we report a density functional theory study of the atomic structure, binding energies, effective coordination numbers, average bond lengths, and magnetic properties of the 3d, 4d, and 5d metal (30 elements) clusters containing 13 atoms, M(13). First, a set of lowest-energy local minimum structures (as supported by vibrational analysis) were obtained by combining high-temperature first- principles molecular-dynamics simulation, structure crossover, and the selection of five well-known M(13) structures. Several new lower energy configurations were identified, e. g., Pd(13), W(13), Pt(13), etc., and previous known structures were confirmed by our calculations. Furthermore, the following trends were identified: (i) compact icosahedral-like forms at the beginning of each metal series, more opened structures such as hexagonal bilayerlike and double simple-cubic layers at the middle of each metal series, and structures with an increasing effective coordination number occur for large d states occupation. (ii) For Au(13), we found that spin-orbit coupling favors the three-dimensional (3D) structures, i.e., a 3D structure is about 0.10 eV lower in energy than the lowest energy known two-dimensional configuration. (iii) The magnetic exchange interactions play an important role for particular systems such as Fe, Cr, and Mn. (iv) The analysis of the binding energy and average bond lengths show a paraboliclike shape as a function of the occupation of the d states and hence, most of the properties can be explained by the chemistry picture of occupation of the bonding and antibonding states.

Intra and interannual variability in the Madeira River water chemistry and sediment load

Concentrations of cations (Na(+), Ca(2+), Mg(2+), K(+), NH(4) (+)), anions (HCO(3) (-), Cl(-), NO(3) (-), SO(4) (2-), PO(4) (3-)) and suspended sediments in the Madeira River water were determined near the city of Porto Velho (RO), in order to assess variation in water chemistry from 2004 to 2007. Calcium and bicarbonate were the dominant cation and anion, respectively. Significant seasonal differences were found, with highest concentrations occurring during the dry season, as expected from the drainage of Andean carbonate-rich substratum. Interannual variations were also observed, but became significant only when annual average discharge was 25% less than normal. Under this atypical discharge condition, bicarbonate was replaced by sulfate, and higher suspended sediment concentrations and loads were also observed. Compared to previously published studies, it appears that no significant changes in water chemistry have occurred during the last 20-30 years, although differences in approaches and sampling designs among this and previous studies may not allow detection of modest changes. The calculated suspended sediment load reported here is close to the values presented elsewhere, reinforcing the relative importance of this river as a sediment supplier for the Amazon Basin. Seasonality has a significant control on the chemistry of Madeira River waters, and severe decrease in discharge due to anthropogenic changes, such as construction of reservoirs or the occurrence of drier years-a plausible consequence of global climate change-may lead to modification in the chemical composition as well in the sediment deliver to the Amazon River.

k(0)-INAA for determining chemical elements in bird feathers

The k(0)-method instrumental neutron activation analysis (k(0)-INAA) was employed for determining chemical elements in bird feathers. A collection was obtained taking into account several bird species from wet ecosystems in diverse regions of Brazil. For comparison reason, feathers were actively sampled in a riparian forest from the Marins Stream, Piracicaba, Sao Paulo State, using mist nets specific for capturing birds. Biological certified reference materials were used for assessing the quality of analytical procedure. Quantification of chemical elements was performed using the k(0)-INAA Quantu Software. Sixteen chemical elements, including macro and micronutrients, and trace elements, have been quantified in feathers, in which analytical uncertainties varied from 2% to 40% depending on the chemical element mass fraction. Results indicated high mass fractions of Br (max=7.9 mgkg(-1)), Co (max= 0.47 mg kg(-1)), Cr (max =68 mg kg(-1)), Hg (max =2.79 mg kg(-1)), Sb (max= 0.20 mg kg(-1)), Se (max=1.3 mg kg(-1)) and Zn (max =192 mg kg(-1)) in bird feathers, probably associated with the degree of pollution of the areas evaluated. In order to corroborate the use of k(0)-INAA results in biomonitoring studies using avian community, different factor analysis methods were used to check chemical element source apportionment and locality clustering based on feather chemical composition. (C) 2010 Elsevier B.V. All rights reserved.

Cadmium telluride nanocrystals as luminescent sensitizers in flow analysis

A fully automated multipumping flow system (MPFS) using water-soluble CdTe quantum dots (QD) as sensitizers is proposed for the chemiluminometric determination of the anti-diabetic drugs gliclazide and glipizide in pharmaceutical formulations. The nanocrystals acted as enhancers of the weak CL emission produced upon oxidation of sulphite by Ce(IV) in acidic medium, thus improving sensitivity and expanding the dynamical analytical concentration range. By interacting with the QD, the two analytes prevented their sensitizing effect yielding a chemiluminescence quenching of the Ce(IV)-SO(3)(2-)CdTe QD system. The pulsed flow inherent to MPFS assured a fast and efficient mixing of all solutions inside the flow cell, circumventing the need for a reaction coil and facilitating the monitoring of the short-lived generated chemiluminescent species. QD crystal size, concentration and spectral region for measurement were investigated. (C) 2011 Elsevier B.V. All rights reserved.

Manufacture of ceramic membranes for application in demulsification process for cross-flow microfiltration

This paper describes the manufacture of tubular ceramic membranes and the study of their performance in the demulsification of soybean oil/water emulsions. The membranes were made by iso-static pressing method and micro and macro structurally characterized by SEM, porosimetry by mercury intrusion and determination of apparent density and porosity. The microfiltration tests were realized on an experimental workbench, and fluid dynamic parameters, such as transmembrane flux and pressure were used to evaluate the process relative to the oil phase concentration (analysed by TOC measurements) in the permeate. The results showed that the membrane with pores` average diameter of 1.36 mu m achieved higher transmembrane flux than the membrane with pores` average diameter of 0.8 mu m. The volume of open pores (responsible for the permeation) was predominant in the total porosity, which was higher than 50% for all tested membranes. Concerning demulsification, the monolayer membranes were efficacious, as the rejection coefficient was higher than 99%.

Manufacture and characterization of ultra and microfiltration ceramic membranes by isostatic pressing

This paper describes the manufacture of tubular UF and MF porous and supported ceramic membranes to oil/water emulsions demulsification. For such a purpose, a rigorous control was realized over the distribution and size of pores. Suspensions at 30 vol.% of solids (zirconia or alumina powder and sucrose) and 70 vol.% of liquids (isopropyl alcohol and PVB) were prepared in a jar mill varying the milling time of the sucrose particles, according to the pores size expected. The membranes were prepared by isostatic pressing method and structurally characterized by SEM, porosimetry by mercury intrusion and measurements of weight by immersion. The morphological characterization of the membranes identified the formation of porous zirconia and alumina membranes and supported membranes. The results of porosimetry analysis by mercury intrusion presented an average pore size of 1.8 mu m for the microfiltration porous membranes and for the ultrafiltration supported membranes, pores with average size of 0.01-0.03 mu m in the top-layer and 1.8 mu m in the support. By means of the manufacture method applied, it was possible to produce ultra and microfiltration membranes with high potential to be applied to the separation of oil/water emulsions. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Drying and autogenous shrinkage of pastes and mortars with activated slag cement

Activated slag cement (ASC) shows significantly higher shrinkage than ordinary Portland cement agglomerates. Cracking generated by shrinkage is one of the most critical drawbacks for broader applications of this promising alternative binder. This article investigates the relationship between ASC hydration, unrestrained drying and autogenous shrinkage of mortar specimens. The chemical and microstructure evolution due to hydration were determined on pastes by thermogravimetric analysis, conduction calorimetry and mercury porosimetry. Samples were prepared with ground blast furnace slag (BFS) activated with sodium silicate (silica modulus of 1.7) with 2.5, 3.5 and 4.5% of Na2O, by slag mass. The amount of activator is the primary influence on drying and autogenous shrinkage, and early hydration makes a considerable contribution to the total result, which increases with the amount of silica. Drying shrinkage occurred in two stages, the first caused by extensive water loss when the samples were exposed to the environment, and the second was associated with the hydration process and less water loss. Due to the refinement of ASC porous system, autogenous shrinkage is responsible for a significant amount of the total shrinkage. (C) 2007 Elsevier Ltd. All rights reserved.

Construction and Evaluation of an Opto-Coupled Potentiostat with a PC/PDA Interface

The design, construction, and characterization of a portable opto-coupled potentiostat are presented. The potentiostat is battery-powered, managed by a microcontroller, which implements cyclic voltammetry (CV) using suitable sensor electrodes. Its opto-coupling permits a wide range of current measurements, varying from mA to nA. Two software interfaces were developed to perform the CV measurement: a virtual instrument for a personal computer (PC) and a C-base interface for personal digital assistant (PDA). The potentiostat has been evaluated by detection of potassium ferrocyanide in KCl medium, both with macro and microelectrodes. There was good agreement between the instrumental results and those from commercial equipment.

Mechanical properties, drying and autogenous shrinkage of blast furnace slag activated with hydrated lime and gypsum

This article reports the characteristics of blast furnace slag (BFS) pastes activated with hydrated lime (5%) and hydrated lime (2%) plus gypsum (6%) in relation to compressive strength, shrinkage (autogenous and drying) and microstructure (porosity, hydrated products). The paste mixtures were characterized using powder X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) and thermogravimetric analysis (TG/DTG). BSF activated with lime and gypsum (LG) results in larger amounts of ettringite when compared with BFS activated with lime (L). Although the porosities of the L and LG mixtures were about the same, there was a greater pore refinement for the BFS activated with lime, with an increase in mesopores volume with age. The presence of ettringite and the higher volumes of macropores cause the compressive strength of BSF activated with hydrated lime plus gypsum to be smaller than that of BFS activated with lime. For both chemical activators, compressive strength developed slowly at early ages. Autogenous and drying shrinkage were greater for the BFS activated with lime, believed to result from the more refined porous structure in comparison with the mixture activated with gypsum plus lime. (c) 2010 Elsevier Ltd. All rights reserved.

Determination of Hg and diet identification in otter (Lontra longicaudis) feces

An analytical procedure for the determination of Hg in otter (Lontra longicaudis) feces was developed, to separate fish scales for the identification of the animal diet. Samples were washed with ultra-pure water and the suspension was sampled and transferred for digestion. The solubilization was performed with nitric-perchloric acid mixture, and detection carried out by the atomic fluorescence spectrometry (AFS). The quality of the analytical procedure was assessed by analyzing in-house standard solutions and certified reference materials. Total Hg concentrations were in the range of 7.6-156 ng g(-1) (July 2004), 25.6-277 ng g(-1) (January 2005) and 14.6-744 ng g(-1) (May 2005) that is approximately the same order of magnitude for all samples collected in two reservoirs at the Tiete River, Brazil. Although Hg concentrations varied with sampling periods and diet, high levels were correlated to the percentage of carnivorous fish scales present in the otter feces. (c) 2007 Elsevier Ltd. All rights reserved.