High current-density anodic electro-dissolution in flow-injection systems for the determination of aluminium, copper and zinc in non-ferroalloys by flame atomic absorption spectrometry

An automatic Procedure with a high current-density anodic electrodissolution unit (HDAE) is proposed for the determination of aluminium, copper and zinc in non-ferroalloys by flame atonic absorption spectrometry, based on the direct solid analysis. It consists of solenoid valve-based commutation in a flow-injection system for on-line sample electro-dissolution and calibration with one multi-element standard, an electrolytic cell equipped with two electrodes (a silver needle acts as cathode, and sample as anode), and an intelligent unit. The latter is assembled in a PC-compatible microcomputer for instrument control, and far data acquisition and processing. General management of the process is achieved by use of software written in Pascal. Electrolyte compositions, flow rates, commutation times, applied current and electrolysis time mere investigated. A 0.5 mol l(-1) HNO3 solution was elected as electrolyte and 300 A/cm(2) as the continuous current pulse. The performance of the proposed system was evaluated by analysing aluminium in Al-allay samples, and copper/zinc in brass and bronze samples, respectively. The system handles about 50 samples per hour. Results are precise (R.S.D < 2%) and in agreement with those obtained by ICP-AES and spectrophotometry at a 95% confidence level.

Evaluation of Bi as internal standard to minimize matrix effects on the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru permanent modifier with co-injection of Pd/Mg(NO3)(2)

Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO3)(2). The correlation coefficient of the graph plotted from the non-nalized absorbance signals of Bi versus Pb was r=0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve, and analytical curves obtained from Pb additions in red and white wine vinegar obtained from reference solutions prepared in 0.2% (v/v) HNO3, samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analvtical curves without. Analytical curves in the 2.5-15 pg L-1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analvte concentration, and typical linear correlations of r=0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 pg L-1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 mu g L-1 and the relative standard deviation was <= 3.8% and <= 8.3% (n = 12) for a sample containing, 10 mu L-1 Pb with and without internal standard, respectively. (C) 2007 Elsevier B.V. All rights reserved.

Determination of vanadium in human hair slurries by electrothermal atomic absorption spectrometry

This work describes an analytical procedure for vanadium determination in human hair slurries by electrothermal AAS using longitudinal heating (LHGA) and transversal heating (THGA) graphite furnace atomizers. The samples were powdered using cryogenic grinding and the hair slurries containing 0.2% (m/v) were prepared in three different media for determination of vanadium: 0.14 mol L-1 HNO3, 0.1% (v/v) Triton X-100 and 0.1% (v/v) water soluble tertiary amines (CFA-C, pH 8). The limits of detection (LOD), limits of quantification (LOQ), and characteristic masses obtained were 0.28, 0.95 mu g L-1 and 35 pg (LHGA) and 0.34, 1.13 mu g L-1 and 78 pg (THGA), respectively. The accuracy of the analytical results obtained by the proposed procedure in both equipments was confirmed by a paired t-test at the 95% confidence level and compared with a conventional procedure based on acid digestion. (c) 2006 Elsevier B.V. All rights reserved.

Reversible intermittent flow-injection determination of mercury in sediments and vinasses by cold vapor atomic absorption spectrometry

A reversible intermittent pow-injection procedure is proposed for the automated determination of mercury in sediments and vinasses by cold vapor atomic absorption spectrometry, CVAAS. Solutions of sample and stannous chloride are carried by two air streams and sequentially injected into the generator/separator chamber in a segmented asynchronous merging zone configuration. The intermittent flow in the forward direction carries the mercury vapor through the flow cell, and in the backward direction, if aspirates the the remaining solution from the vessel to waste. We investigated composition and concentration of reagents, pow rates, commutation times, reactor configuration, and conditions for mercury release. The accuracy was checked by mercury determination in a certified sediment and spiked vinasses and river waters. The system handles about 100 samples per hour (0.50-5.00 mu g L-1), consuming ca. 2.5 mL of sample and 50 mg of SnCl2 per determination; Good recoveries (92-103%) were obtained with spiked samples. Results are precise (RSD <3% for 2.5 mu g Hg L-1, n = 12) and in agreement with values for certified reference material at 95% confidence level. (C) 1999 John Wiley & Sons, Inc.

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.

Arsenic as internal standard to correct for interferences in the determination of antimony by hydride generation in situ trapping graphite furnace atomic absorption spectrometry

The feasibility of using internal standardization (IS) to correct for interferences in hydride generation with in situ trapping in graphite furnace was evaluated. Arsenic was chosen as internal standard for Sb determination and Ir was used as permanent modifier. Fluctuations in the main parameters that affect the analytical results were minimized by IS and an effective contribution was verified in the studies of liquid phase interferences. Cobalt and Ni2+ were selected to illustrate the potential use of IS on the correction of interference by transition metals. The application of IS allows the Sb determination in samples containing up to 20-fold higher concentration of the Co2+ and Ni2+ when compared to the procedure without IS. The relative standard deviation of measurements varied from 0.3% to 0.7% and from 1.1% to 3.2% with and without IS, respectively. Recoveries within 92% and 107% of spiked aqueous solution containing Sb(III) and Sb(V) were found. (c) 2005 Elsevier B.V. All rights reserved.

Evaluation of different rhodium modifiers and coatings on the simultaneous determination of As, Bi, Pb, Sb, Se and of Co, Cr, Cu, Fe, Mn in milk by electrothermal atomic absorption spectrometry

Different kinds of modifiers and coatings on the integrated platform of transversely heated graphite atomizer (THGA) have been tested for the simultaneous determination of two group of elements: the first, the more volatile, formed by arsenic, bismuth, lead, antimony and selenium; the second, the less volatile, formed by cobalt, chromium, cupper, iron and manganese in milk by electrothermal atomic absorption spectrometry. Different Rh-modifiers were studied, such as Rh-coated platforms (Rh), carbide plus rhodium coated platforms (W-Rh, Zr-Rh), carbide-coated platforms (W and Zr) with co-injection of RhCl3, solutions and uncoated platforms with injection of solutions of Pd(NO3)(2), Mg(NO3)(2), and RhCl3. Milk samples were diluted 1:10 in 1.0% HNO3 and injected into the tube. The mass of modifier deposited and co-injected in the tube and the use of end capped tubes were also evaluated in order to improve the electrothermal behavior of analytes. Integrated platform pretreated with W plus co-injection RhCl3 for first group and pretreated with W-Rh for second group were elected. For 20 mu L injected samples the analytical curves in the 5.0-20.0 mu g L-1 concentration range have good linear correlation coefficients (r > 0.998). Relative standard deviations (n = 12) are < 6% and the calculated characteristic masses are between 5 pg and 62 pg.

Deviation from the sech2 superradiant emission law in a two-level atomic system

The atomic superradiant emission is treated in the single-particle mean-field approximation. A single-particle Hamiltonian, which represents a dressed two-level atom in a radiation field, can be obtained and it is verified that it describes the transient regime of the emission process. While the line-shape emission for a bare atom follows the sech2 law, for the dressed atom the line shape deviates appreciably from this law and it is verified that the deviation depends crucially on the ratio of the dynamic frequency shift to the transition frequency. This kind of deviation is observed in experimental results. © 1990 The American Physical Society.

Determination of mercury in agroindustrial samples by flow-injection cold vapor atomic absorption spectrometry using ion exchange and reductive elution

A flow-injection system with a Chelite-S® cationic resin packed minicolumn is proposed for the determination of trace levels of mercury in agroindustrial samples by cold vapor atomic absorption spectrometry. Improved sensitivity and selectivity are attained since mercuric ions are on-line concentrated whereas other potential interferents are discarded. With on-line reductive elution procedure, concentrated hydrochloric acid could be replaced by 10% w/v SnCl2, in 6 M HCl as eluent. The reversed-intermittent stream either carries the atomic mercury, to the flow cell in the forward direction or removes the residue from reactor/gas liquid separator to a discarding flask in the opposite direction. Concentration and volume of reagent, acidity, flow rates, commutation times and potential interfering species were investigated. For 120 s preconcentration time, the proposed system handles about 25 samples h-1 (50.0 500 ng l-1), consuming about 10 ml sample and 5 mg SnCl2 per determination. The detection limit is 0.8 ng l-1 and the relative standard deviation (RSD) (n = 12) of a 76.7 ng l-1 sample is about 5%. Results are in agreement with certified value of standard materials at 95% confidence level and good recoveries (97-128%) of spiked samples were found. (C) 2000 Elsevier Science B.V.

Coherent atomic oscillations and resonances between coupled Bose-Einstein condensates with time-dependent trapping potential

The atomic tunneling between two tunnel-coupled Bose-Einstein condensates (BECs) in a double-well time-dependent trap was studied. For the slowly varying trap, synchronization of oscillations of the trap with oscillations of the relative population was predicted. Using the Melnikov approach, the appearance of the chaotic oscillations in the tunneling phenomena between the condensates was confirmed.

Can four-fermion contact interactions at one-loop explain the new atomic parity violation results?

We investigate the possibility that four-fermion contact interactions give rise to the observed deviation from the standard model prediction for the weak charge of cesium, through one-loop contributions. We show that the presence of loops involving the third generation quarks can explain such a deviation.

Analytical functions for the calculation of hyperspherical potential curves of atomic systems

We present angular basis functions for the Schrödinger equation of two-electron systems in hyperspherical coordinates. By using the hyperspherical adiabatic approach, the wave functions of two-electron systems are expanded in analytical functions, which generalizes the Jacobi polynomials. We show that these functions, obtained by selecting the diagonal terms of the angular equation, allow efficient diagonalization of the Hamiltonian for all values of the hyperspherical radius. The method is applied to the determination of the 1S e energy levels of the Li + and we show that the precision can be improved in a systematic and controllable way. ©2000 The American Physical Society.