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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 pyrrolidine-dithiocarbamate (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) 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).

Rapid Speciation Analysis of Cr(VI) and Cr(III) by Reversed-Phase High-Performance Liquid Chromatography with UV Detection