A method for the separation and speciative determination of Cr(VI) and Cr(III) has been developed. The procedure is based on coprecipitation of Cr(III) on 3-ethyl-4-(p-chlorobenzylidenamino-4,5-dihydro-1 H-1,2,4-triazol-5-one (EPHBAT) without carrier element. The Cr(III) can be selectively precipitated on EPHBAT in the pH range of 8.0-9.0, while Cr(VI) cannot be retained. Total chromium was determined after the reduction of Cr(VI) to Cr(III) with 0.5 mL of concentrated H2SO4 and 0.5 mL of ethanol. Cr(VI) concentrations were obtained as the respective differences between total chromium and Cr(III). Experiments were performed to optimize conditions, such as pH, amounts of EPHBAT, sample volume. etc. A preconcentration factor of 50-fold was achieved for Cr(III). The detection limit of the method for Cr(III) was 1.0 mu g L-1. To validate the developed method, the certified reference materials (NIST SRM 1573a and GBW 0703) were analyzed. The method was applied for the speciation of chromium in spiked natural water samples with satisfactory results. (C) 2009 Elsevier B.V. All rights reserved.