SPECIATION OF CR(VI)/CR(III) BY ELECTROTHERMAL ATOMIZATION AAS AFTER ELECTRODEPOSITION ON A LVOV PLATFORM

The pyrolysed graphite L'vov platform of a tube furnace is considered as an electrode for the electrodeposition and speciation of chromium by electrothermal atomisation atomic absorption spectrometry (ETA-AAS). Firstly, a preliminary study of the Cr(VI)/Cr(III) voltammetric behavior at pH 4.70 on a glassy-carbon electrode is carried out. Secondly, the L'vov platform is used as a cathodic macro-electrode for the selective preconcentration of Cr(VI)/Cr(III) on a mercury film. Speciation of Cr(VI)/Cr(III) is carried out on the basis of the electrolysis potential (E(e)): at pH 4.70 and E(e) = -0.30 V, only Cr(VI) is reduced to Cr(III) and accumulated as Cr(OH)3 by adsorption on a mercury film; at E(e) = -1.80 V both Cr(VI) and Cr(III) are accumulated forming an amalgam with added mercury(II) ions. Once the film has been formed, the platform is transferred to a graphite tube to atomise the element. The reliability of the method was tested for the speciation of chromium in natural waters and it proves to be highly sensitive thanks to the electroanalytical step. In all samples, the Cr(VI) concentration was less than the detection limit (0. 1 5 ng ml-1), and the concentration of Cr(III) agrees with those of total chromium. The analytical recovery of Cr(VI) added to water samples [3.50 ng ml-1 of Cr(VI)] was 105 +/- 6.2%.