A simple and rapid method is developed for the simultaneous determination of Cr(VI) and Cr(III) based on the formation of their different complexes with ammonium pyrrolidinedithiocarbamate (APDC). Separation is performed using reversed-phase high-performance liquid chromatography coupled with UV detection. The conditions for complex formation and speciation are determined, such as solution pH, amount of APDC, temperature, and type of mobile phase. In order to substantially reduce the analysis time, the separation is carried out without extraction of chromium-APDC complexes from the mother liquor. Under the optimum analysis conditions, the chromatograms obtained show good peak separation, and the absolute detection limits (3σ σ) are 2.2 µg/L for Cr(VI) and 4.5 µg/L for Cr(III). The calibration curves are linear from 3 to 5000 µg/L for Cr(VI) and 5 to 3000 µg/L for Cr(III). The relative standard deviations of peak areas in five measurements using a sample solution of 200 µg/L are less than 2% for Cr(VI) and 4% for Cr(III), indicating good reproducibility for this analytical method. Furthermore, simultaneous determination of Cr(VI) and Cr(III) is successful with the application of the proposed procedure in the synthetic wastewaters containing common heavy metal ions: Fe(III), Pb(II), Cd(II), Cu(II), and Zn(II).
IntroductionSpeciation analysis of an element gives information about the individual concentrations of its various chemical forms. Speciation of chromium has attracted researchers' interest because of the high toxicity of its compounds and their widespread use in metallurgy, refractory, and chemical industries (1). Two common oxidation states of chromium are present in the environment, and their physicochemical properties are each drastically different from those of the other (1,2). Trivalent chromium, Cr(III), is essential for the maintenance of the normal glucose tolerance factor (3), whereas hexavalent chromium, Cr(VI), is a well-known carcinogen. The maximum permissible concentrations of chromium compounds in wastewaters are established as 0.5 mg/L for Cr(III) and 0.1 mg/L for Cr(VI) (USPS). Therefore, quantitative analysis of Cr(VI) and Cr(III) with low concentration levels is needed for environmental studies, as well as for industrial effluent controls.Different analytical techniques for chromium speciation with atomic and molecular spectroscopy or voltammetry have been reported in the literature (1-11). In most methods, Cr(VI) can be determined directly, and then the Cr(III) concentration is calculated from the difference between Cr(VI) and the total chromium concentration. Because this calculation may induce some uncertainty (6), much attention in recent years has been focused on simultaneous determination methods of chromium compounds with different oxidation states, such as ion-chromatography (2,6,12), ion-pair chromatography (IPC) (2), and reversed-phase (RP) chromatography (4,11,13,14). For online detection, high sensitivity and better selectivity can be achieved by using RP high-performance liqu...