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.

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.

Determination of cadmium in river water samples by flame AAS after on-line preconcentration in mini-column packed with 2-aminothiazole-modified silica gel

A rapid and sensitive method was developed to determine trace levels of Cd2+ ions in an aqueous medium by flame atomic absorption spectrometry, using on-line preconcentration in a mini-column packed with 100 mg of 2-aminothiazol modified silica gel (SiAT). The Cd2+ ions were sorbed at pH 5.0. The preconcentrated Cd2+ ions were directly eluted from the column to the spectrometer's nebulizer-burner system using 100 μL of 2 mol L-1 hydrochloric acid. A retention efficiency of over 95% was achieved. The enrichment factor (calculated as the ratio of slopes of the calibration graphs) obtained with preconcentrations in a mini-column packed with SiAT (A = -1.3 × 10-3 + 1.8 × 10-3 [Cd2+]) and without preconcentrations (A = 4 × 10-5 + 3.5 × 10-3[Cd2+]), was 51 and the detection limit calculated was 0.38 μg L-1. The preconcentration procedure was applied to determine trace levels of Cd in river water samples. The optimum preconcentration conditions are discussed herein.

Determination of vanadium in urine by electrothermal atomic absorption spectrometry using hot injection and preconcentration into the graphite tube

In this work it was developed a procedure for the determination of vanadium in urine samples by electrothermal atomic absorption spectrometry using successive injections for preconcentration into a preheated graphite tube. Three 60 μL volumes were sequentially injected into the atomizer preheated to a temperature of 110°C. Drying and pyrolysis steps were carried out after each injection. A chemical modifier, barium difluoride (100 mg L-1), and a surfactant, Triton X-100 (0.3% v v-1), were added to the urine sample. When injecting into a hot graphite tube, the sample flow-rate was 0.5 μL s-1. The limits of detection and quantification were 0.54 and 1.82 without preconcentration, and 0.11 and 0.37 μg L-1 with preconcentration, respectively. The accuracy of the procedure was evaluated by an addition-recovery experiment employing urine samples. Recoveries varied from 96.0 to 103% for additions ranging from 0.8 to 3.5 μg L-1 V. The developed procedure allows the determination of vanadium in urine without any sample pretreatment and with minimal dilution of the sample.

Rapid determination of zinc in foods by flow injection analysis with flame AAS using gradient calibration method

A calibration method was developed using flow injection analysis (FI) with a Gradient Calibration Method (GCM). The method allows the rapid determination of zinc In foods (approximately 30 min) after treatment with concentrated sulphuric acid and 30% hydrogen peroxide, and analysis with flame atomic absorption spectrometry (FAAS). The method provides analytical results with a relative standard deviation of about 2% and requires less time than by conventional FI calibration. The electronic selection of different segments along the gradient and monitoring of the technique covers wide concentration ranges while maintaining the inherent high precision of flow injection analysis. Concentrations, flow rates, and flow times of the reagents were optimized in order to obtain best accuracy and precision. Flow rates of 10 mL/min were selected for zinc. In addition, the system enables electronic dilution and calibration where a multipoint curve can be constructed using a single sample injection.

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 calcium by atomic absorption spectrophotometry applied to the preparation of alginate:chitosan complexes

Polysaccharicles, as alginate and chitosan, have been used to obtain modified release dosage forms. Alginate, due to its property of building gels during the complex formation with calcium ions, allows the building of capsules containing a core constituted by calcium alginate. This work had for objective to determine the appropriate calcium concentration for the preparation of alginate-chitosan capsules, by means of calcium quantification using atomic absorption spectrophotometry. The methodology of calcium quantification was validated through analysis of the limit of detection, precision, accuracy and recovery of the method. The capsules, containing or not the drug, were prepared by the complex coacervation/ionotropic gelification method. Calcium was quantified after samples mineralization and dilution in lantanium solution. The results showed that the amount of calcium incorporated into the capsules depends on the amount of calcium added to the medium, and this ratio increases until the concentration of 1.5% of initial calcium chloride and above this concentration there is a decrease in the proportion of calcium bonded. It was observed that the proportion of calcium that links to the polymer is inversely proportional to the amount of calcium added. The calcium amount incorporated depends on the concentration of the polymeric dispersions used as well as on the ratio between the two polymers.

Evaluation of Ir-based modifiers in the simultaneous determination of As, Bi, Pb, Sb, and Se in milk by graphite furnace atomic absorption spectrometry

Different modifiers (IrCl3, W+IrCl3, Zr+IrCl 3) and coatings (Ir, W-Ir, Zr-Ir) were evaluated for the simultaneous determination of arsenic, bismuth, lead, antimony, and selenium in milk by graphite furnace atomic absorption spectrometry using the 'end-capped' transversely heated graphite atomizer (THGA). Integrated platform, pretreated with Zr-Ir as permanent modifier, was elected as the optimum surface modification resulting in up to 250 firings. Two additional recoatings were possible without significant changes in the analytical performance (750 firings). For 20 μL of matrix-matched standard solutions using diluted (1:10) milk samples, typical correlation coefficients between integrated absorbance and analyte concentration (5.00-20.0 μg/L) was always better than 0.999. The levels of the analytes found in commercial milk samples were lower than the limit of detection: 2.9 μg/L As, 2.9 μg/L Bi, 1.8 μg/L Pb, 1.9 μg/L Sb, and 2.5 μg/L Se. Recoveries were found within the following intervals: 88-114% for As, 89-118% for Bi, 89-113% for Pb, 91-115% for Sb, and 92-115% for Se. The relative standard deviations (n = 12) were ≤2% (As), ≤ 5% (Bi), ≤ 1.4% (Pb), ≤ 3% (Sb), and 5% (Se), and the respective calculated characteristic masses were 54 pg As, 55 pg Bi, 40 pg Pb, 56 pg Sb, and 51 pg Se.

Determination of copper in fish feed by graphite furnace atomic absorption spectrometry using slurry sampling

The present work develops and optimizes a method to determine copper in samples of feces and fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube coated internally with metallic rhodium and tungsten carbide that acts as chemical modifiers. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of copper) were 0.24 and 0.79 μg L -1 for the standard feces slurries and 0.26 and 0.87 μg L -1 for the standard feed slurries. The proposed method was applied in studies of absorption of copper in different fish feeds and their results proved compatible with that obtained from samples mineralized by acid digestion using microwave oven. © Springer Science+Business Media, LLC 2008.

Determination of lead in eye shadow and blush by high-resolution continuum source graphite furnace atomic absorption spectrometry employing directSolid sampling

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

Simultaneous determination of chromium and nickel in medicinal plants by slurry sampling graphite furnace atomic absorption spectrometry

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