Dispersive micro-solid phase extraction with a magnetic nanocomposite followed by electrothermal atomic absorption measurement for the speciation of thallium

Abstract A magnetic dispersive micro-solid phase extraction procedure for the determination of the thallium content in waters is presented. The incorporation in the sample (10 mL) of a small amount of graphene-Fe3O4 composite (3.6 mg) in the presence of 10−4 mol L−1 Aliquat 336 at pH 2 results in the complete retention of both thallium(I) and thallium(III). After separation with a magnet, the micro-solid phase recovered is treated with 0.05 mL of a 0.1 mol L−1 sodium ethylenediaminetetracetate solution at pH 9, and the supernatant obtained after application of the magnet is introduced in the electrothermal atomizer of an atomic absorption spectrometer to obtain the signal corresponding to the total thallium content. For speciation, the trivalent form in a second sample aliquot is separated by means of a liquid-liquid extraction stage with chloroform and methyl trioctyl ammonium in the presence of bromide, and the signal corresponding to the monovalent form is obtained, the concentration of thallium(III) being obtained by difference. The enrichment factor is 185, which permits a detection limit as low as 0.01 μg L−1 of the analyte to be achieved. The relative standard deviation for five measurements at the 0.1 μg L−1 thallium level is below 5%. The reliability of the procedure is verified by analysing five certified reference samples for which speciation data are also given.