Analytical procedure for total mercury determination in fishes and shrimps by chronopotentiometric stripping analysis at gold film electrodes after microwave digestion

A method for the total mercury determination in fish and shrimps employing chronopotentiometric stripping analysis on gold film electrodes is described. Fish and shrimp tissues were digested using a microwave oven equipped with closed vessels. We developed a microwave heating program which decomposed all the samples employing diluted nitric acid and hydrogen peroxide. The proposed method was validated by analyzing a certified reference material and then applied for different fish species from fresh water and seawater acquired in local markets of São Paulo city, Brazil. The Brazilian legislation establishes 0.5 and 1 mg per kilogram of fish as upper limit of mercury for omnivorous and predator species, respectively. Except for blue shark tissues, the mercury content was situated below 0.5 mu g g(-1) for all the analyzed samples. The detection limit of the proposed method was calculated as 5 ng g(-1) of sample utilizing 5 minutes of electrodeposition (+300 mV vs. Ag/AgCl) on the gold electrode. (c) 2006 Elsevier Ltd. All rights reserved.

The effects of bacterial leaching on metal partitioning in sewage sludge

The partitioning of Mn, Al, Zn, Cu and Ti ions in municipal sewage sludge was investigated before and after bioleaching processes effectuated by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. Oxidation reduction potential increase and pH decrease were obtained as a result of bacterial activity. A less pronounced and constant decrease was obtained with A. ferrooxidans, whereas A. thiooxidans presented a lag phase before a steep pH decrease. Metal solubilization was accomplished in experimental systems supplemented with energy source, Fe2+ for A. ferrooxidans and S-0 for A. thiooxidans. Solubilization efficiency differed for each metal except for Al, and was relatively similar for either organism. Metal partitioning was conducted using five-step sequential extraction procedure before and after the bioleaching. The results indicated that Zn and Mn ions were mostly associated with the organic fraction, whereas Cu, Al and Ti ions with the sulphide/ residue fraction. The bioleaching process caused prompt solubilization of metals mostly associated with the more labile fractions (exchangeable, adsorbed and organically bound metals), whereas those associated to the less labile ones (EDTA and sulphide/residue fractions) were exchanged towards more labile fractions.

Unilamellar vesicles obtained by simply mixing dioctadecyldimethylammonium chloride and bromide with water

Optically clear dispersions of dioctadecyldimethylammonium bromide and chloride (DODAX, X = Br-, Cl-) in water can be obtained by simply mixing the amphiphiles at low concentrations (I mM) and at a temperature safely above the gel to liquid crystalline phase transition temperature (T-m approximate to 45-48 degrees C) of DODAX in water. Under these conditions, dynamic light scattering shows that, at room temperature, the dispersions contain two well-defined populations of large vesicles with average hydrodynamic radii (RH) of 80 and 337 nm for DODAB and of 69 and 247 nm for DODAC. Cryo-transmission electron microscopy (cryo-TEM) micrographs show that DODAX vesicles are unilamellar and polydisperse with apparent radius up to 800 nm. The vesicles are stable for at least I month according to the ageing time-dependence of the turbidity and molar absorption coefficient. (c) 2006 Elsevier B.V.. All rights reserved.

Biological leaching of Mn, Al, Zn, Cu and Ti in an anaerobic sewage sludge effectuated by Thiobacillus ferrooxidans and its effect on metal partitioning

The chemical fractionation and bioleaching of Mn, At, Zn, Cu and Ti in municipal sewage sludge were investigated using Thiobacillus ferrooxidans as leaching microorganism. As a result of the bacterial activity, ORP increase and pH reduction were observed. Metal solubilization was accomplished only in experimental systems supplemented with energy source (Fe(II)). The solubilization efficiency approached similar to80% for Mn and Zn, 24% for Cu, 10% for At and 0.2% for Ti. The chemical fractionation of Mn, At, Zn, Cu and Ti was investigated using a five-step sequential extraction procedure employing KNO3. KF, Na4P2O7, EDTA and HNO3. The results show that the bioleaching process affected the partitioning of Mn and Zn, increasing its percentage of elution in the KNO3 fraction while reducing it in the KF, Na4P2O7 and EDTA fractions. No significant effect was detected on the partitioning of Cu and Al. However, quantitatively the metals Mn, Zn, Cu and At were extracted with higher efficiency after the bacterial activity. Titanium was unaffected by the bioleaching process in both qualitative and quantitative aspects. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

BACTERIAL LEACHING OF URANIUM ORE FROM FIGUEIRA-PR, BRAZIL, AT LABORATORY AND PILOT-SCALE

A bacterial leaching program was carried out in order to evaluate the potential of applying this process to leach uranium from the ore of Figueira-PR, Brazil. The experiments were carried out in shake flasks, column percolation (laboratory and semipilot scale) and in heap leaching. In shake flasks and in column percolation experiments at laboratory scale, bacterial activity on the ore was confirmed: approximately 60% of uranium was leached, against around 30% in sterilized controls. Column percolation experiments at semipilot scale and heap leaching (850 tons of ore) showed uranium extractions of approximately 50%. In both experiments, a complementary sulfuric acid attack, after the bacterial leaching phase, was necessary to reach this level of uranium extraction.

Morphological analysis of pits formed on Al 2024-T3 in chloride aqueous solution

It has been used a new image analysis method, based on segmentation by shape parameters, for pits morphology examination from Al 2024 aluminum-copper alloy in chloride aqueous solution. Corrosion behavior of this alloys in naturally aerated 3.5% NaCl solution has been investigated through open circuit potential measurements. Afterwards, pits have been characterized by image analysis taking density and size measurements right from corroded surfaces. Morphological investigation has been conducted for profiles, cut orthogonally from mean surface planes, and observed through light microscopy. Image analysis data could demonstrate that pits are wider than deep, evoluting for conical, quasi-conical or irregular shapes. Most pits have presented a quasi-conical morphology, but the wider ones have evoluted to an irregular shape influenced by sub-surface microstructure. Image analysis based on shape segmentation could enhance the differences on morphological behavior. (C) 2004 Elsevier B.V. All rights reserved.

Fast ultrasound-assisted treatment of urine samples for chronopotentiometric stripping determination of mercury at gold film electrodes

This work describes an efficient, fast, and reliable analytical methodology for mercury determination in urine samples using stripping chronopotentiometry at gold film electrodes. The samples were sonicated in the presence of concentrated HCl and H2O2 for 15 min in order to disrupt the organic ligands and release the mercury. Thirty samples can be treated over the optimized region of the ultrasonic bath. This sample preparation was enough to allow the accurate stripping chronopotentiometric determination of mercury in the treated samples. No background currents and no passivation of the gold film electrode due to the sample matrix were verified. The samples were also analyzed by cold vapour atomic absorption spectrometry (CV-AAS) and good agreement between the results was verified. The analysis of NIST SRM 2670 (Toxic Metals in Freeze-Dried Urine) also validated the proposed electroanalytical method. Finally, this method was applied for mercury evaluation in urine of workers exposed to hospital waste incinerators. (c) 2006 Elsevier B.V. All rights reserved.

Sympathetic hyperactivity, respiratory failure, pruritus, and anesthesia after unintentional epidural injection of potassium chloride: Case report

Background and Objectives. A combination of epidural and general anesthesia has been widely used to attenuate the surgical stress response and to provide postoperative analgesia. This case report illustrates the use of this anesthetic technique. Analgesia was induced with local anesthetic in the immediate postoperative period using unintentional 19.1% potassium chloride (KCI) as diluent. Methods. An ASA I male patient was scheduled for surgical correction of idiopathic megaesophagus under continuous epidural anesthesia combined with general anesthesia. In the postoperative period, while preparing 10 mt 0.125% bupivacaine to be administered through the epidural catheter for pain control, 5 mt 19.1% KCI was unintentionally used as diluent, resulting in a 9.55% potassium solution concentration. Results. The patient developed warmness of the lower limbs, tachycardia, hypertension, intense pruritus on the chest, agitation, exacerbation of sensory and motor blocks, and respiratory failure secondary to pulmonary edema, requiring ventilatory support. Total recovery was observed after 24 hours. Conclusions. Epidurally injected potassium leads to severe clinical manifestations caused by autonomic dysfunction, spinal cord irritation, and possible release of histamine. Despite continuous recommendations, ampule misidentification still happens in hospitals, frequently leading to serious accidents.

Compact disks, a new source for gold electrodes. Application to the quantification of copper by PSA

In this work we describe a versatile and very sensitive way for copper quantification by potentiometric stripping analysis using gold electrodes obtained from recordable compact disks (CDs). This new source of electrodes (CDtrodes) shown similar performance to the commercial gold electrodes with superior versatility and lower cost. Recordable CDs contains a highly pure gold film with thickness between 50 and 100 nm and superficial area of ca. 100 cm(2). The working electrode developed was used successfully in stationary cell and many experimental parameters have been optimized. For copper, the detection limit attained was 30 ng L-1 (600 s deposition time) with remarkable precision (standard deviation of 1.8 % for 20 repetitive measurements using 25 mu gL(-1) of copper with 60 s of deposition time). The gold electrode developed was used for analysis of copper in sugar cane spirits and tap water samples. The results were compared with those obtained by atomic absorption spectroscopy.

Amperometric differential determination of ascorbic acid in beverages and vitamin C tablets using a flow cell containing an array of gold microelectrodes modified with palladium

A simple and attractive method for quantification of ascorbic acid (AA) in beers, soda, natural juices and commercial vitamin C tablets was achieved by combining Bow injection analysis and amperometric detection. An array of gold microelectrodes electrochemically modified by deposition of palladium was employed as working electrode which was almost unaffected by fouling effects. Ascorbic acid was quantified in beverages and vitamin tablets using amperometric differential measurements. This method is based on three steps involving the flow injection of: 1) the sample plus a standard addition of AA, 2) the pure sample, and 3) the enzymatically-treated sample. The enzymatic treatment was carried out with Cucumis sativus tissue, which is a rich source of ascorbate oxidase, at pH 7. The calibration plots for freshly prepared ascorbic acid standards were very linear in the concentration range of 0.18-1.8 mg L-1 with a relative standard deviation (RSD) < 1%, while for real samples the deviations were between 2.7% to 8.9%.

Aggregation behaviour of hydrophobically modified poly(allylammonium) chloride

The behaviour of hydrophobically modified poly(allylammonium) chloride having octyl, decyl, dodecyl and hexadecyl side chains has been studied in aqueous solution using fluorescence emission techniques. Micropolarity studies using the I-1/I-3 ratio of the vibronic bands of pyrene show that the formation of hydrophobic microdomains depends on both the length of the side chain and the polymer concentration. The I-1/I-3 ratio of the polymers with low hydrophobe content (less than 5% mel) changes substantially when reaching a certain concentration. These changes are assigned to aggregation originating from interchain interactions. This behaviour is also confirmed by the behaviour of the monomer/excimer emission intensities of pyrene- dodecanoic acid used as a probe. For polymers having dodecyl side chains and hydrophobe contents higher than 10%, aggregates are formed independently of the polymer concentration. Anisotropy measurements show that microdomains resulting from the inter- and/or intramolecular interactions are similar to those observed for cationic surfactants. Viscosity measurements show that the coil dimensions are substantially decreased for the polymers having high hydrophobe contents, indicating intramolecular associations.