In the present work, a solid phase extraction system has been proposed for speciation of Cr(III) and Cr(VI) in the real samples. The procedure based on the adsorption of chromium(III) as dithizonate chelate on the Chromosorb 108 resin. After reduction of Cr(VI) by concentrated H2SO4 and ethanol, the system was applied to the total chromium. Cr(VI) was calculated as the difference between the total Cr content and the Cr(HI) content. The influences of the analytical parameters including pH of the aqueous solution, amounts of dithizone, eluent type, sample volume and flow rates of the sample and eluent solution were investigated. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The adsorption capacity of sorbent was 4.50 mg/g Cr(III). The detection limit of Cr(III) is 0.75 mu g/L. The proposed method was applied to the speciation of chromium in environmental samples including natural waters and total chromium preconcentration in microwave digested Turkish tobacco, coffee and soil samples with satisfactory results. In order to verify the accuracy of the method, two certified reference materials (NIST SRM 1573a Tomato Leaves and RTC-CRM 025-050 Metals on Soil) were analyzed and the results obtained were in good agreement with the certified values. The relative errors and relative standard deviations were below 5% and 9%, respectively. (c) 2005 Elsevier B.V. All rights reserved.