Direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirits by graphite furnace AAS using Tungsten permanent modifier with Co-injection of Pd/Mg(NO3)(2)

A method was developed using the multi-element graphite furnace atomic absorption spectrometry technique for the direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirit (cachaqa) samples. Also employed was the end-capped transversely heated graphite atomizer (THGA) with platforms pre-treated with W permanent modifier and co-injection of Pd/Mg(NO3)(2). Pyrolysis and atomization temperature curves were established in a cachaqa medium (1+1; v/v) containing 0.2% (v/v) HNO3 and spiked with 20 mu g L-1 As and Pb and 200 mu g L-1 Cu. The effect of the concentration of major elements usually present in cachaqa matrices (Ca, Mg, Na, and K) and ethanol on the absorbance of As, Cu, and Pb was investigated. Analytical working solutions of As, Cu, and Pb were prepared in 10% (v/v) ethanol plus 5.0 mg L-1 Ca, Mg, Na, and K. Acidified to 0.2% (v/v) HNO3, these solutions were suitable to build calibration curves by matrix matching. The proposed method was applied to the simultaneous determination of As, Cu, and Pb in commercial sugar cane spirits. The characteristic mass for the simultaneous determination was 16 pg As, 119 pg Cu, and 28 pg Pb. The pretreated tube lifetime was about 450 firings. The limit of detection (LOD) was 0.6 mu g L-1 As, 9.2 mu g L-1 Cu, and 0.3 pig L-1 Pb. The found concentrations varied from 0.81 to 4.28 mu g L-1 As, 0.28 to 3.82 mg L-1 Cu and 0.82 to 518 mu g L-1 Pb. The recoveries of the spiked samples varied from 94-112% (As), 97-111% (Cu), and 95-101% (Pb). The relative standard deviation (n=12) was 6.9%, 7.4%, and 7.7% for As, Cu, and Pb, respectively, present in a sample at 0.87 mu g L-1, 0.81 mg L-1, and 38.9 mu g L-1 concentrations.

Direct determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by simultaneous GFAAS using integrated platforms pretreated with W-Rh permanent modifier together with Pd plus Mg modifier

A method is proposed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by electrothermal atomic absorption spectrometry (ETAAS) using W-Rh permanent modifier together with Pd(NO3)(2) + Mg(NO3)(2) conventional modifier. The integrated platform of a transversely heated graphite atomizer (THGA) was treated with tungsten, followed by rhodium, forming a deposit containing 250 mug W + 200 mug Rh. A 500-muL, volume of fuel ethanol was diluted with 500 muL, of 0.14 mol L-1 HNO3 in an autosampler cup of the spectrometer. Then, 20 muL, of the diluted ethanol was introduced into the pretreated graphite platform followed by the introduction of 5 mug Pd(NO3)(2) + 3 mug Mg(NO3)(2). The injection of this modifier was required to improve arsenic and iron recoveries in fuel ethanol. Calibrations were carried out using multi-element reference solutions prepared in diluted ethanol (1 + 1, v/v) acidified to 0. 14 mol L-1 HNO3. The pyrolysis and atomization temperatures of the heating program were 1200degreesC and 2200degreesC, respectively, which were obtained with multielement reference solutions in acidic diluted ethanol (1 + 1, v/v; 0. 14 mol L-1 HNO3). The characteristic masses for the simultaneous determination in ethanol fuel were 78 pg Al, 33 pg As, 10 pg Cu, 14 pg Fe, 7 pg Mn, and 24 pg Ni. The lifetime of the pretreated tube was about 700 firings. The detection limits (D.L.) were 1.9 mug L-1 Al, 2.9 mug L-1 As, 0.57 mug L-1.Cu, 1.3 mug L-1 Fe, 0.40 mug L-1 Mn, and 1.3 mug L-1 Ni. The relative standard deviations (n = 12) were 4%, 4%, 3%, 1.5%, 1.2%, and 2.2% for Al, As, Cu, Fe, Mn, and Ni, respectively. The recoveries of Al, As, Cu, Fe, Mn, and Ni added to the fuel ethanol samples varied from 81% to 95%, 80% to 98%, 97% to 109%, 85% to 107%, 98% to 106% and 97% to 103%, respectively. Accuracy was checked for the Al, As, Cu, Fe, Mn, and Ni determination in 10 samples purchased at a local gas station in Araraquara-SP City, Brazil. A paired t-test showed that at the 95% confidence level the results were in agreement with those obtained by single-element ETAAS.

Tangential-flow ultrafiltration: a versatile methodology for determination of complexation parameters in refractory organic matter from Brazilian water and soil samples

In this work the copper(II) complexation parameters of aquatic organic matter, aquatic and soil humic substances from Brazilian were determined using a new versatile approach based on a single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods. The results regarding the copper(II) complexation capacity and conditional stability constants obtained for humic materials were compared with those obtained using direct potentiometry with a copper-ion-selective electrode. The analytical procedure based on ultrafiltration is a good alternative to determine the complexation parameters in natural organic material from aquatic and soil systems. This approach presents additional advantages such as better sensibility, applicability for multi-element capability, and its possible to be used under natural conditions when compared with the traditional ion-selective electrode.

Direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirits by graphite furnace AAS using tungsten permanent modifier with co-injection of Pd/Mg(N03)2

A method was developed using the multi-element graphite furnace atomic absorption spectrometry technique for the direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirit (cachaça) samples. Also employed was the end-capped transversely heated graphite atomizer (THGA) with platforms pre-treated with W permanent modifier and co-injection of Pd/Mg(N03)2. Pyrolysis and atomization temperature curves were established in a cachaça medium (1+1; v/v) containing 0.2% (v/v) HN03 and spiked with 20 μg L-1 As and Pb and 200 μg L-1Cu. The effect of the concentration of major elements usually present in cachaça matrices (Ca, Mg, Na, and K) and ethanol on the absorbance of As, Cu, and Pb was investigated. Analytical working solutions of As, Cu, and Pb were prepared in 10% (v/v) ethanol plus 5.0 mg L-1 Ca, Mg, Na, and K. Acidified to 0.2% (v/v) HNO3, these solutions were suitable to build calibration curves by matrix matching. The proposed method was applied to the simultaneous determination of As, Cu, and Pb in commercial sugar cane spirits. The characteristic mass for the simultaneous determination was 16 pg As, 119 pg Cu, and 28 pg Pb. The pretreated tube lifetime was about 450 firings. The limit of detection (LOD) was 0.6 μg L-1As, 9.2 μg L-1 Cu, and 0.3 μg L-1Pb. The found concentrations varied from 0.81 to 4.28 μg L-1As, 0.28 to 382 mg L-1 Cu and 0.82 to 518 μg L-1 Pb. The recoveries of the spiked samples varied from 94-112% (As), 97-111% (Cu), and 95-101% (Pb). The relative standard deviation (n=12) was 6.9%, 7.4%, and 7.7% for As, Cu, and Pb, respectively, present in a sample at 0.87 μgL-1, 0.81 mgL-1, and 38.9 μgL-1concentrations.

Improving synthetic aperture image by image compounding in beamforming process

In this work, signal processing techniques are used to improve the quality of image based on multi-element synthetic aperture techniques. Using several apodization functions to obtain different side lobes distribution, a polarity function and a threshold criterium are used to develop an image compounding technique. The spatial diversity is increased using an additional array, which generates complementary information about the defects, improving the results of the proposed algorithm and producing high resolution and contrast images. The inspection of isotropic plate-like structures using linear arrays and Lamb waves is presented. Experimental results are shown for a 1-mm-thick isotropic aluminum plate with artificial defects using linear arrays formed by 30 piezoelectric elements, with the low dispersion symmetric mode S0 at the frequency of 330 kHz. © 2011 American Institute of Physics.

Definição da assinatura geoquímica multielemento secundária dos depósitos Canoas e Perau - Vale do Ribeira - PR e sua aplicação como ferramenta na seleção de novas áreas potenciais para pesquisa mineral

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Evolução metamórfica P-T-t da porção norte do complexo Guaxupé na região de Arceburgo - Santa Cruz da Prata, MG

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise de dados pedogeoquímicos de multielementos visando o refinamento de mapeamento geológico de detalhe em alvos de Pb-Zn nos municípios de Adrianópolis, Cerro Azul e Tunas do Paraná (Vale do Ribeira, PR)

In order to to research, the region of Perau, base metal mineralization, Grupo Votorantim Metals conducted a soil sampling on targets predetermined holding its chemical analysis. These reviews have been provided by the company for this work was to evaluate the potential use of these data pedogeochemical multi-element for refinement of the work of geological mapping. We selected six targets: Varginha, Salvador, Guararema Taquara Lisa and Coffin of Mendes, in the municipalities of Adrianople, Cerro Azul and Tunas do Paraná, located in Vale do Ribeira (PR). Both have about 10 km2 and situated in the geological context of the Fold Belt Terrane and the Massif de Joinville. The main rock types are present metasedimentary rocks of low to medium grade metamorphic, interspersed the amphibolites ortoderivados, both belonging to the Complex Perau, gneisses and migmatitic Complex. Applied to the geochemical data descriptive statistical techniques (variogram, kriging and histogram). From the correlation between the distributions of elements with the geological data, we could assess the potential of the proposed methodology.

Determinação da sensibilidade elementar de amostras-padrão pelo método de flurescência de raios X por reflexão total

To determinate the multielemental concentrations in biological samples using the technique of total reflection X-ray fluorescence (TRFX) is essential the use of standard samples. The aim of this study is the determination of the sensitivities of the relevant elements in standard samples (Multi Element atomic spectroscopy standard solution in HNO3 I) prepared in three solutions with different and known concentrations. Based on the sensitivities of the elements contained in the multilelementar standard sample, it can estimate the sensitivity for an element found in the biological sample and consequently it is possible to determinate the concentration, even though the standard does not contain this element. The measurement of fluorescence was performed at the Brazilian Synchrotron Light Laboratory (LNLS) in Campinas

Archaeofacies Analysis: Using Depositional Attributes to Identify Anthropic Processes of Deposition in a Monumental Shell Mound of Santa Catarina State, Southern Brazil

In the coast of Santa Catarina State (southern Brazil), a large population of monumental shell mounds characterizes a highly dynamic coastal setting. In this paper, sedimentary facies analysis was adapted for description, sampling, and interpretation of shell mound complex and repetitive archaeostratigraphic successions. Archaeofacies identification in the field, according to depositional attributes, is tested by contrasting field description with multi-element chemical analyses, total carbon and nitrogen determinations, and micromorphological descriptions. Two vertical sequences at the black deposit of Jabuticabeira II shell mound were studied and preliminary results showed that: (1) depositional attributes are a reliable base for archaeofacies identification in the field, (2) the formation process of this site involved a sequence of anthropic depositional processes, where burned refuse was redeposited over the shell mound following a ritual construction pattern, and (3) the black deposit includes a double palimpsest that refers to provenance and meaning of mound construction material. (C) 2009 Wiley Periodicals, Inc.

Determination of trace elements in bovine semen samples by inductively coupled plasma mass spectrometry and data mining techniques for identification of bovine class

The reproductive performance of cattle may be influenced by several factors, but mineral imbalances are crucial in terms of direct effects on reproduction. Several studies have shown that elements such as calcium, copper, iron, magnesium, selenium, and zinc are essential for reproduction and can prevent oxidative stress. However, toxic elements such as lead, nickel, and arsenic can have adverse effects on reproduction. In this paper, we applied a simple and fast method of multi-element analysis to bovine semen samples from Zebu and European classes used in reproduction programs and artificial insemination. Samples were analyzed by inductively coupled plasma spectrometry (ICP-MS) using aqueous medium calibration and the samples were diluted in a proportion of 1:50 in a solution containing 0.01% (vol/vol) Triton X-100 and 0.5% (vol/vol) nitric acid. Rhodium, iridium, and yttrium were used as the internal standards for ICP-MS analysis. To develop a reliable method of tracing the class of bovine semen, we used data mining techniques that make it possible to classify unknown samples after checking the differentiation of known-class samples. Based on the determination of 15 elements in 41 samples of bovine semen, 3 machine-learning tools for classification were applied to determine cattle class. Our results demonstrate the potential of support vector machine (SVM), multilayer perceptron (MLP), and random forest (RF) chemometric tools to identify cattle class. Moreover, the selection tools made it possible to reduce the number of chemical elements needed from 15 to just 8.

Entwicklung und Validierung einer massenspektrometrischen Isotopenverdünnungsanalyse zur direkten Multielementbestimmung in pulverförmigen Proben mittels LA-ICP-MS

In dieser Arbeit wurde erstmalig eine massenspektrometrische Isotopenverdünnungsanalyse (MSIVA) als Quantifizierungsmethode für die Multielementbestimmung in pulverförmigen Proben mittels Laserablations-induktiv gekoppelter Plasma-Massenspektrometrie (LA-ICP-MS) entwickelt. Diese LA-ICP-MSIVA wurde zur Bestimmung von Elementspuren in optisch-reinem Calciumfluorid eingesetzt und anhand der Analyse mehrerer zertifizierter Referenzmaterialien unterschiedlicher Matrixzusammensetzung validiert.Mit den in dieser Arbeit entwickelten direkten LA-ICP-MS-Analysenmethoden dürfte es in der Zukunft möglich sein, Routineanalysen von optisch-reinem Calciumfluorid durchzuführen, wobei sich im Vergleich zu naßchemischen Aufschlußverfahren eindeutige Vorteile ergeben. Neben einer deutlich einfacheren und weniger kontaminationsanfälligen Probenvorbereitung liegen die Nachweisgrenzen (im Bereich von 0.05 ng/g für Zr bis 20 ng/g für Mg) um etwa ein bis drei Größenordnungen niedriger.Die am Beispiel der Multielementbestimmung in Calciumfluorid entwickelte LA-ICP-MSIVA wurde nachfolgend anhand der Analyse von sieben zertifizierten Referenzmaterialien mit organischer und anorganischer Matrix validiert. Hierbei wurde für 28 von insgesamt 32 analysierten Elementkonzentrationen eine hervorragende Übereinstimmung mit den zertifizierten Werten erhalten. Im Mittel weichen die mittels LA-ICP-MSIVA analysierten Gehalte nur um 1.6 % von den zertifizierten Werten ab. Die erzielte Präzision von durchschnittlich 4.9 % relativer Standardabweichung für drei unabhängig analysierte Proben liegt im Bereich der durchschnittlichen zertifizierten Unsicherheit der Referenzmaterialien von 4.4 %.

Silicon Photonics Integrated Circuits for Flexible Optical Systems

This dissertation deals with the design and the characterization of novel reconfigurable silicon-on-insulator (SOI) devices to filter and route optical signals on-chip. Design is carried out through circuit simulations based on basic circuit elements (Building Blocks, BBs) in order to prove the feasibility of an approach allowing to move the design of Photonic Integrated Circuits (PICs) toward the system level. CMOS compatibility and large integration scale make SOI one of the most promising material to realize PICs. The concepts of generic foundry and BB based circuit simulations for the design are emerging as a solution to reduce the costs and increase the circuit complexity. To validate the BB based approach, the development of some of the most important BBs is performed first. A novel tunable coupler is also presented and it is demonstrated to be a valuable alternative to the known solutions. Two novel multi-element PICs are then analysed: a narrow linewidth single mode resonator and a passband filter with widely tunable bandwidth. Extensive circuit simulations are carried out to determine their performance, taking into account fabrication tolerances. The first PIC is based on two Grating Assisted Couplers in a ring resonator (RR) configuration. It is shown that a trade-off between performance, resonance bandwidth and device footprint has to be performed. The device could be employed to realize reconfigurable add-drop de/multiplexers. Sensitivity with respect to fabrication tolerances and spurious effects is however observed. The second PIC is based on an unbalanced Mach-Zehnder interferometer loaded with two RRs. Overall good performance and robustness to fabrication tolerances and nonlinear effects have confirmed its applicability for the realization of flexible optical systems. Simulated and measured devices behaviour is shown to be in agreement thus demonstrating the viability of a BB based approach to the design of complex PICs.

Inductive-Capacitive Resonant Circuit Sensors for Structural Health and Environmental Monitoring

Inductive-capacitive (LC) resonant circuit sensors are low-cost, wireless, durable, simple to fabricate and battery-less. Consequently, they are well suited to sensing applications in harsh environments or in situations where large numbers of sensors are needed. They are also advantageous in applications where access to the sensor is limited or impossible or when sensors are needed on a disposable basis. Due to their many advantages, LC sensors have been used for sensing a variety of parameters including humidity, temperature, chemical concentrations, pH, stress/pressure, strain, food quality and even biological growth. However, current versions of the LC sensor technology are limited to sensing only one parameter. The purpose of this work is to develop new types of LC sensor systems that are simpler to fabricate (hence lower cost) or capable of monitoring multiple parameters simultaneously. One design presented in this work, referred to as the multi-element LC sensor, is able to measure multiple parameters simultaneously using a second capacitive element. Compared to conventional LC sensors, this design can sense multiple parameters with a higher detection range than two independent sensors while maintaining the same overall sensor footprint. In addition, the two-element sensor does not suffer from interference issues normally encountered while implementing two LC sensors in close proximity. Another design, the single-spiral inductive-capacitive sensor, utilizes the parasitic capacitance of a coil or spring structure to form a single layer LC resonant circuit. Unlike conventional LC sensors, this design is truly planar, thus simplifying its fabrication process and reducing sensor cost. Due to the simplicity of this sensor layout it will be easier and more cost-effective for embedding in common building or packaging materials during manufacturing processes, thereby adding functionality to current products (such as drywall sheets) while having a minor impact on overall unit cost. These modifications to the LC sensor design significantly improve the functionality and commercial feasibility of this technology, especially for applications where a large array of sensors or multiple sensing parameters are required.

Rare earth elements determined in Antarctic ice by inductively coupled plasma

Inductively coupled plasma mass spectrometry (ICP-MS) is a suitable tool for multi-element analysis at low concentration levels. Rare earth element (REE) determinations in standard reference materials and small volumes of molten ice core samples from Antarctica have been performed with an ICP-time of flight-MS (ICP-TOF-MS) system. Recovery rates for REE in e.g. SPS-SW1 amounted to not, vert, similar ~103%, and the relative standard deviations were 3.4% for replicate analysis at REE concentrations in the lower ng/l range. Analyses of REE concentrations in Antarctic ice core samples showed that the ICP-TOF-MS technique meets the demands of restricted sample mass. The data obtained are in good agreement with ICP-Quadrupole-MS (ICP-Q-MS) and ICP-Sector Field-MS (ICP-SF-MS) results. The ICP-TOF-MS system determines accurately and precisely REE concentrations exceeding 5 ng/l while between 0.5 and 5 ng/l accuracy and precision are element dependent.