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.

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.

The improvement of thin polymer film properties through plasma immersion ion implantation and deposition technique

Thin polymer films were deposited from acetylene and argon mixtures by plasma immersion ion implantation and deposition. The effect of the pulse frequency, v, on molecular structure, optical gap, contact angle and hardness of the films was investigated. It was observed progressive dehydrogenation of the samples and increment in the concentration of unsaturated carbon bonds as the pulse frequency was increased. Film hardness and contact angle increased and optical gap decreased with v. These results are interpreted in terms of the chain unsaturation and crosslinking.

Asymmetrical penetration of microwave in a conducting media and determination of microwave conductivity for very thin samples using electron spin resonance

Dyson's theory of conduction electron spin resonance (CESR) has been used in the limit d less than or equal to delta (d being the thickness of the sample and delta the skin depth of the microwave field) to obtain the microwave conductivity from the (A/B) ratio of the CESR absorbed power derivative. In this work we calculate the CESR absorbed power derivative using Kaplan's approach and show that the (A/B) ratio can be enhanced if asymmetrical penetration of microwave is used, which means that the microwave field enters into the sample from one of the faces. Therefore, the determination of the microwave conductivity from the (A/B) ratio of the CESR line can be performed for thinner samples. Experimentally, asymmetrical penetration can be obtained if one of the sample's faces is covered with a thin gold layer. The determination of microwave conductivity in conducting polymers films is among the possible applications of this method. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

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.

Chronopotentiometric stripping analysis using gold electrodes, an efficient technique for mercury quantification in natural waters

This paper proposes a simple methodology for mercury quantification in natural water by stripping chronopotentiometry at constant current, using gold (film) electrodes constructed from recordable CDs in stationary cell. The proposed method allows the direct measurement of labile mercury in natural waters. To quantify total mercury, a robust and low cost UV irradiation system was developed for the degradation of organic constituents of water. The proposed system presents such advantages as excellent sensitivity, low cost, versatility, and smaller dimensions (portability for on-field applications) when compared with other techniques (ICP, GFAAS, fluorimetry) traditionally utilized for mercury quantification. A large linear region of responses was observed, situated over the range 0.02 - 200 μ g L-1. Various experimental parameters were optimized and the system allowed quantifications in natural samples, with detection limit of 8 ng L-1 and excellent reproducibility (RSD of 1.4% for 48 repetitive measurements using a 10 μ g L-1 mercury solution). Different metal ions were evaluated, including copper, as possible interferences on stripping mercury signals. Applications of the new method were demonstrated for the analysis of certified and groundwater samples spiked with a known amount of mercury and for the quantification of methylmercury in synthetic oceanic water, originally utilized for fishes contamination experiment.

Ferroelectric SBN thin films grown by an SBN/Bi2O3 PLD sequential process

Ferroelectric SrBi2Nb2O9 (SBN) thin films were prepared by pulsed laser deposition (PLD) on Pt/Ti/SiO2/Si(100) using a sequential deposition process from two SBN and Bi2O3 targets. This route allows for bismuth enrichment of the film composition in order to improve the ferroelectric characteristics. Structural and microstructural characterizations were performed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The composition of films and targets was determined by energy dispersive X-ray spectrometry (EDX). The deposition temperature, which provided well-crystallized layered perovskite SBN phase films in situ, was found to be 700°C. The results were compared with those obtained for SBN films deposited at 400°C and then crystallized ex situ. For an ex situ annealing temperature of 750°C, a remanent polarization value (Pr) of 23.2 μc/cm2 and a coercive field (Ec) of 112 kV/cm were measured. © 2001 Elsevier Science Ltd. All rights reserved.

Optical, mechanical and surface properties of amorphous carbonaceous thin films obtained by plasma enhanced chemical vapor deposition and plasma immersion ion implantation and deposition

Diverse amorphous hydrogenated carbon-based films (a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:Si:O) were obtained by radiofrequency plasma enhanced chemical vapor deposition (PECVD) and plasma immersion ion implantation and deposition (PIIID). The same precursors were used in the production of each pair of each type of film, such as a-C:H, using both PECVD and PIIID. Optical properties, namely the refractive index, n, absorption coefficient, α, and optical gap, ETauc, of these films were obtained via transmission spectra in the ultraviolet-visible near-infrared range (wavelengths from 300 to 3300 nm). Film hardness, elastic modulus and stiffness were obtained as a function of depth using nano-indentation. Surface energy values were calculated from liquid drop contact angle data. Film roughness and morphology were assessed using atomic force microscopy (AFM). The PIIID films were usually thinner and possessed higher refractive indices than the PECVD films. Determined refractive indices are consistent with literature values for similar types of films. Values of ETauc were increased in the PIIID films compared to the PECVD films. An exception was the a-C:H:Si:O films, for which that obtained by PIIID was thicker and exhibited a decreased ETauc. The mechanical properties - hardness, elastic modulus and stiffness - of films produced by PECVD and PIIID generally present small differences. An interesting effect is the increase in the hardness of a-C:H:Cl films from 1.0 to 3.0 GPa when ion implantation is employed. Surface energy correlates well with surface roughness. The implanted films are usually smoother than those obtained by PECVD. ©2013 Elsevier B.V. All rights reserved.

Scanned stripping chronopotentiometry at bismuth film rotating disc electrodes: a method for quantitative dynamic metal speciation

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

Gold electrodes from recordable CDs for mercury quantification by flow injection analysis

The development of a new methodology for the construction of very efficient flow cells for mercury detection by potentiometric stripping analysis, employing the thin gold layer of recordable CDs as working electrode is reported. This new source of electrodes (CDtrodes) show very attractive performance, similar to that obtained with commercial gold electrodes, with superior versatility. The low cost of this new source of gold electrodes allows a frequent replacement of the electrode, avoiding cumbersome clean-up treatments. Various experimental parameters have been optimized to yield low detection limits (0.25 ng/mL of mercury for 5 min deposition at 0.3 V) and good precision (standard deviation of 1.9% was obtained for 15 repetitive measurements using 10 ng/mL of mercury). Standard curves were found to be linear over the range of 0.5-100 μg L-1 of mercury. The flow cells developed were used for the quantification of mercury in oceanic and tap water. © Springer-Verlag 2000.

A label-free immunosensor based on recordable compact disk chip for early diagnostic of the dengue virus infection

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Utilização de um eletrodo de grafite-epóxi recoberto com [Zn(FEN)3][tetratris(4-clorofenil) borato]2 sensível a zinco(II) em meio 1,10-fenantrolina como eletrodo indicador em titulações potenciométricas de precipitação

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

Contribution to the study of the solid-state reaction of mercury with pure rhodium

Thermogravimetry (TG) and other analysis techniques (EDX, SEM, Mapping surface, X-ray diffraction, inductively coupled argon plasma emission spectroscopy and atomic spectrometry with cold vapor generation) were used to study the reaction of Hg with Rh. The results permitted the suggestion that, when subjected to heat, an electrodeposited Hg film reacts with Rh to form intermetallic products with different stabilities, as indicated by at least three mass loss steps. In the first step, between room temperature and 160°C, only the bulk Hg is removed. From this temperature up to about 175°C, the mass loss can be attributed to the desorption of a film of metallic Hg. The last step, from 175 to 240°C, can be ascribed to the removal of Hg from a thin dark film of RhHg2.

Plasmonic structures fabricated by interference lithography for sensor applications

In this work we demonstrate the use of holographic lithography for generation of large area plasmonic periodic structures. Submicrometric array of holes, with different periods and thickness, were recorded in gold films, in areas of about 1 cm2, with homogeneity similar to that of samples recorded by Focused Ion Beam. In order to check the plasmonic properties, we measured the transmission spectra of the samples. The spectra exhibit the typical surface plasmon resonances (SPR) in the infrared whose position and width present the expected behavior with the period of the array and film thickness. The shift of the peak position with the permittivity of the surrounding medium demonstrates the feasebility of the sample as large area sensors. © 2009 SPIE.

Anisotropy in the transport properties of type II superconducting films with periodic pinning

Using numerical simulations, we analyze the anisotropy effects in the critical currents and dynamical properties of vortices in a thin superconducting film submitted to hexagonal and Kagomé periodical pinning arrays. The calculations are performed at zero temperature, for transport currents parallel and perpendicular to the main axis of the lattice, and parallel to the diagonal axis of the rhombic unit cell. We show that the critical currents and dynamic properties are anisotropic for both pinning arrays and all directions of the transport current. The anisotropic effects are more significant just above the critical current and disappear with higher values of current and both pinning arrays. The dynamical phases for each case and a wide range of transport forces are analyzed. © 2012 Springer Science+Business Media, LLC.