Feasibility of internal standardization in the direct and simultaneous determination of As, Cu and Pb in sugar-cane spirits by graphite furnace atomic absorption spectrometry

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

Internal standardization in graphite furnace atomic absorption spectrometry: Comparative use of As and Ge to minimize matrix effects on Se determination in milk

Arsenic and germanium have been evaluated as internal standards to minimize matrix effects on the direct determination of selenium in milk by graphite furnace atomic absorption spectrometry (GFAAS) using tubes with integrated platform, pre-treated with W together with I'd as chemical modifier. The efficiency of As and Ge as internal standards for 25 mu g L-1 Se plus 500 mu g (L)-1 As or Ge in diluted (1 + 9 v/v) milk plus 1.0% (v/v) HNO3 was evaluated by means of correlation graphs plotted from the normalized absorbance signals (n = 20) of internal standard (axis gamma) versus analyte (axis x). The equations that describe the linear regression were: A(As)= - 0.004 +/- 0.019 +/- 1.02 + 0.019 A(Se) (r=0.9967 +/- 0.005); A(Ge)= - 0.0 17 +/- 0.015 + 1.01 +/- 0.015 A(Se) (r = 0.9978 +/- 0.004). Samples and reference solutions were automatically spiked with 500 mu g L-1 Ge or As and 1.0% (v/v) HNO3 by the autosampler. For 20 mu L of aqueous standard solutions, analytical curves in the 5.00-40.0 mu g L-1 Se range were established using the ratio of Se absorbance to internal standard absorbance (A(Se)A(IS)) versus analyte concentration, and good linear correlations were obtained. The characteristic mass was 40 pg Se. Limits of detection were 0.55 and 0.40 mu g L-1 with As and Ge as the internal standard, respectively. Relative standard deviations (RSD) for a sample containing 25 mu g L-1 Se were 1.2% and 1.0% (n = 12) using As and Ge, respectively. The RSD without internal standardization was about 6%. The accuracy of the proposed method was evaluated by an addition-recovery experiment and all recovered values were in the 99-105% range with IS and in the 70-80% range without IS. Using Ge as the internal standard, results of analysis of standard reference materials were in agreement with certified values at a 95% confidence level. The selenium concentration for 10 analyzed milk samples varied from 5.0 to 20 mu g L-1. (c) 2005 Elsevier B.V. All rights reserved.

Standardization of platelet parameters determination in blood samples collected with EDTA

The Abbott Cell-Dyn 3000 automated hematological analyzer prepares a histogram of platelet volume, which is measured by a technique using electrical impedance, inferring from its platelet count (PLT), mean platelet volume (MPV) and platelet distribution width (PDW). This equipment also calculates the plateletcrit (PCT). These platelet parameters may be important to evaluate platelet function, but they require standardization, because platelets swell when in contact with ethylenediaminetetra-acetic acid salts, hence an increase in blood sample storage time produces artificially increased results. To assess the effect of storage time on MPV, PLT, PDW and PCT, blood samples from 23 sickle cell anemia patients during steady state (Group I) and 50 from healthy controls (Group II) were placed in Vacutainer® tubes with dipotassium ethylenediaminetetra-acetic acid and measured over a period of 1440 minutes (24 h) at the following times: immediately after the venipuncture (time 0), 15, 30, 60, 120, 240, 360, 480 and 1440 minutes. The mean values of MPV and PCT were significantly increased (p<0.00001) along the storage time in both groups. The mean values of PLT and PDW were practically stable (p>0.05) throughout the storage time in both groups.

Use of the internal standardization for difficult sampling by graphite furnace atomic absorption spectrometry

This work shows the potentiality of As as internal standard to compensate errors from sampling of sparkling drinking water samples in the determination of selenium by graphite furnace atomic absorption spectrometry. The mixture Pd(NO 3) 2/Mg(NO 3) 2 was used as chemical modifier. All samples and reference solutions were automatically spiked with 500 μg l -1 As and 0.2% (v/v) HNO 3 by the autosampler, eliminating the need for manual dilutions. For 10 μl dispensed sample into the graphite tube, a good correlation (r=0.9996) was obtained between the ratio of analyte absorbance by the internal standard absorbance and the analyte concentrations. The relative standard deviations (R.S.D.) of measurements varied from 0.05 to 2% and from 1.9 to 5% (n=12) with and without internal standardization, respectively. The limit of detection (LD) based on integrated absorbance was 3.0 μg l -1 Se. Recoveries in the 94-109% range for Se spiked samples were obtained. Internal standardization (IS) improved the repeatability of measurements and increased the lifetime of the graphite tube in ca. 15%. © 2004 Elsevier B.V. All rights reserved.

Determination of potassium and sodium in an ash sample by gamma-ray spectroscopy

Neutron activation analysis and gamma-ray spectroscopy were used to determine the quantity of potassium and sodium in an ash sample of Tabebuia sp bombarded with thermal neutrons. These techniques, widely applied in nuclear physics, can be used in the context of wood science as an alternative for the usual physical chemistry methods applied in this area. The quantity of K and Na in an 8.60 +/- 0.10 mg of ash was determined as being 1.3 +/- 0.3 mg and 11.0 +/- 1.8 mu g, respectively. The ratio of Tabebuia sp converted into ash was also determined as 0.758 +/- 0.004%.

Dependence of the electrical conductivity and elastomeric properties on sample preparation of blends of polyaniline and natural rubber

Blend films (free-standing) containing 20% in volume of polyaniline (PANI) in 80% of natural rubber (NR) were fabricated by casting in three different ways: (1) adding PANI-EB (emeraldine base) dissolved in N-methyl-2-pyrrolidone (NMP) to the latex (NRL), (2) adding PANI-EB dissolved in in-cresol to NR dissolved in xylol (NRD), (3) overlaying the surface of a pure NR cast film with a PANI layer grown by in situ polymerization (NRO). All the films were immersed into HCl solution to achieve the primary doping (protonation) of PANI before the characterization. The main goal here was to investigate the elastomeric and electrical conductivity properties for each blend, which may be applied as pressure and deformation sensors in the future. The characterization was carried out by optical microscopy, dc conductivity, vibrational spectroscopy (infrared absorption and Raman scattering), thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and tensile stress-strain curves. The results suggest that the NRL blend is the most suitable in terms of mechanical and electrical properties required for applications in pressure and deformation sensors: a gain of conductivity without losing the elastomeric property of the rubber. (c) 2005 Wiley Periodicals, Inc.

Off line extraction of phenol from human urine sample with isoamyl alcohol and determination by HPLC

This method has been developed for extraction and determination of phenol in a urine sample by high performance liquid chromatography.After acid hydrolysis, the free phenol was extracted with isoamyl alcohol solvent, followed by back extraction with 0.5 mol.L-1 sodium hydroxide solution and analyzed by an isocratic HPLC Varian System, equipped with reverse-phase column (MicroPak-C-18). The mobile phase was acetonitrile in 0.01 mol.L-1 hydrochloric acid solution, (20:80 v/v), and at a now-rate of 1.0 mL.min-1. The chromatogram was monitored at 220 nm in room temperature. The identification was based on retention time and the quantification was performed by automatic peak-area determination, corrected for the external standards method.The recovery was higher than 99.5 % for phenol and reproducibility of method was shown to be 2.3% standard deviation and 5.6% coefficient of variance (n=20). The limit detection was 0.05 mgL(-1) and a range of 0.05 to 20.0 mgL(-1) of phenol for linearity.

A control chart based on sample ranges for monitoring the covariance matrix of the multivariate processes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A new chart based on sample variances for monitoring the covariance matrix of multivariate processes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The Synthetic Control Chart Based on Two Sample Variances for Monitoring the Covariance Matrix

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The double sampling and the EWMA charts based on the sample variances

We propose a new statistic to control the covariance matrix of bivariate processes. This new statistic is based on the sample variances of the two quality characteristics, in short VMAX statistic. The points plotted on the chart correspond to the maximum of the values of these two variances. The reasons to consider the VMAX statistic instead of the generalized variance vertical bar S vertical bar is its faster detection of process changes and its better diagnostic feature; that is, with the VMAX statistic it is easier to identify the out-of-control variable. We study the double sampling (DS) and the exponentially weighted moving average (EWMA) charts based on the VMAX statistic. (C) 2008 Elsevier B.V. All rights reserved.

Preconcentration and determination of Cu(II) in a fresh water sample using modified silica gel as a solid-phase extraction adsorbent

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

Standardization of an experimental model of parabiotic isolated heart in rabbits

O objetivo foi a padronização de modelo experimental de coração isolado parabiótico em coelhos, testando sua estabilidade e durabilidade, para fins de pesquisa cardiovascular. Foram utilizados 66 coelhos raça Norfolk-2000 divididos em grupo doador do coração isolado e animais suporte, totalizando 33 preparações. Mediante auxilio de bombas peristálticas estabeleceu-se suporte circulatório para o coração isolado mantendo-se fluxo constante(16ml/min.). Um balão intraventricular foi inserido no ventrículo esquerdo, sendo ajustado para gerar pressão diastólica de ± 10mmHg. A freqüência foi fixada em 120 batimentos por minuto mediante o uso de marcapasso. Foram avaliadas variáveis hemodinâmicas, laboratoriais e anatomopatológicas. Das 33 preparações, 13 foram excluídas mediante critérios pré-estabelecidos. Das 20 restantes, 10 cumpriram o tempo máximo do protocolo(180 minutos). Com relação ao animal suporte houve deterioração hemodinâmica progressiva c/ queda da pressão arterial média(89,30±6,09mmHg->47,50±6,35mmHg). Com relação ao corações isolado, das 10 preparações que cumpriram os 180 minutos de protocolo, houve estabilidade hemodinâmica. As variáveis laboratoriais mostraram queda progressiva do sódio, potássio e hemoglobina, sendo compatível com hemodiluição. O exame anatomopatológico mostrou espaçamento maior entre fibras, compatível com edema. O presente modelo mostrou estabilidade e atividade de 100% das preparações em 60 minutos, havendo perdas progressivas chegando a 50% das preparações em atividade em 180 minutos. O presente modelo, dentro das limitações estabelecidas é viável para pesquisas cardiovasculares.