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The present work describes the mass spectrometric detection of organometallic compounds following their atmospheric pressure ionization using a commercial direct analysis in real time (DART) ion source. Several organometallic compounds of As, Fe, Hg, Pb, Se, and Sn were examined, and their corresponding mass spectra as well as induced fragmentation patterns were recorded. Gas phase sampling of the pure organometallic compounds or their solutions prepared in toluene generated temporally stable signals. For the majority of the compounds, the molecular ion or protonated molecule was detected; noticeable exceptions are the tetra-substituted compounds for which their less-substituted species dominated. The organometallic species were used as model compounds for a systematic investigation of the impact of operating parameters of the DART source, including gas temperature and electrode voltages. In general, results have shown that powering the electrodes designed to remove ions from the DART gas stream results in a reduction in signal intensity for most of the compounds investigated, suggesting that charged species from the plasma play an important role in the ionization process of the test analytes.

A fast routine screening method for the simultaneous determination of cadmium and iron in bean and soil samples is proposed, using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling. The primary absorption line at 228.802 nm has been used for the determination of cadmium, and an adjacent secondary line, at 228.726 nm, for iron. Fourteen bean samples and 10 soil samples from nine states all over Brazil have been analyzed. The limits of detection (3 sigma, n = 10) were 2.0 microg kg(-1) for Cd and 4.5 mg kg(-1) for Fe. The relative standard deviation ranged from 4 to 7% for Cd and from 5 to 28% for Fe, which is usually acceptable for a screening method. The accuracy of the method has been confirmed by the analysis of two certified reference materials; the results were in agreement with the certified values at a 95% confidence interval.

A simple and highly selective flow injection on-line pre-concentration and separation-flame atomic absorption spectrometric method was developed for routine analysis of trace amounts of lead in biological and environmental samples. The selective preconcentration of lead was achieved in a wide range of sample acidity (0.075 to > or = 3 mol L(-1)HNO3) on a microcolumn (145 microL) packed with a macrocycle immobilized on silica gel. The lead retained on the column was effectively eluted with an EDTA solution (0.03 mol L(-1), pH 10.5). Three kinds of potential interferences, i.e., preconcentration inferences from metal ions with an ionic radius similar to that of Pb(II) due to their competition for the cavity of the macrocyle, elution kinetic interferences from ions which form stable complexes with EDTA due to their competition for EDTA, and interferences in the atomizer from residual matrix, were evaluated and compared in view of the read-out mode of the analyte response (peak area vs peak height), column wash step (with vs without), column capacity (50 vs 145 microL), and column shape (conical vs cylindrical). The results showed that a combination of increase in column capacity, quantitation based on peak area, and use of dilute nitric acid for column wash before elution efficiently avoid the above-mentioned potential interferences. With the use of a 145 microL column the present system tolerated up to 0.1 g L(-1) Ba(II), 1 g L(-1) Sr(II), and at least 10 g L(-1) Fe(III), Cu(II), Ni(II), Zn(II), Cd(II), Al(III), K(I), Na(I), CaII), and Mg(II) in the sample digest. Further improvement of the interference tolerance can be achieved by increasing column capacity if more complicated samples need to be analyzed. At a sample loading rate of 3.9 mL min(-1) with 30-s preconcentration, an enrichment factor of 52, a detection limit (3s) of 5 micrograms L(-1) Pb in the digest and a sampling frequency of 63 h(-1) were obtained. The precision (RSD, n = 11) at the 200 micrograms L(-1) level was 1.9%. The enrichment factor and the detection limit can be further improved by increasing sample loading rate without degradation in the efficiency due to the favorable kinetics and low hydrodynamic impedance of the present system. The analytical results obtained by the proposed method for a number of biological and environmental standard reference materials were in good agreement with the certified and recommended values.

A flow injection manifold with an air-segmented and air-transported operational sequence for on-line coupling of microcolumn separation and preconcentration to electro-thermal atomic absorption spectrometry (ETAAS) was developed for the determination of (ultra)trace selenite and selenate in water. The determination of selenite was achieved by selective reaction with pyrrolidine dithiocarbamate (PDC), sorption of the resultant Se-PDC compound onto a conical microcolumn (10.2 microL) packed with RP C18 sorbent, elution with ethanol, and detection by ETAAS. The concentration of selenate was obtained as the difference between the concentrations of selenite after and before prereduction of selenate to selenite. With the developed manifold and operation sequence,the dispersion during elution and eluate transport and the eluent volume required for complete elution of the sorbed analyte were minimized. As a result, the sorbed analyte was quantitatively eluted from the column with only 26 microL of ethanol, and all the eluate was automatically introduced into the graphite tube by an air flow without the need of preheating the graphite tube or precise timing. Pretreatment of the graphite tube with iridium as a long-term "permanent" modifier effectively prevented analyte loss arising from the high volatility of the Se-PDC compound and greatly improved the precision, sensitivity, and detection limit. One thermal pretreatment of the graphite tube with injection of 150 microgram of iridium made possible at least 200 repetitive atomization cycles. With a preconcentration time of 180 s and a sample flow rate of 1.4 mL min(-1), an enhancement factor of 112 was achieved in comparison with direct injection of 30 microL of aqueous solution. The detection limit (3s) was 4.5 ng L(-1)Se. The RSD (n = 7) was 3.8% at 20 ng L(-1)Se. The concentrations of selenite and selenate determined in synthetic aqueous mixtures were in good agreement with the expected values. The recoveries for selenite from spiked seawater samples ranged from 98 to 102%. The concentrations of selenite in several seawater reference materials obtained with simple aqueous standard solutions for calibration agreed well with the certified and information values, respectively. In addition, the developed method was successfully applied to the certification of selenite and selenate in water.