Application of a macrocycle immobilized silica gel sorbent to flow injection on-line microcolumn preconcentration and separation coupled with flame atomic absorption spectrometry for interference-free determination of trace lead in biological and environmental samples.

Abstract

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.