A new, simple, rapid and sensitive separation, preconcentration and speciation procedure for chromium in environmental liquid and solid samples has been established. The present speciation procedure for Cr(III) and Cr(VI) is based on combination of carrier element-free coprecipitation (CEFC) and flame atomic absorption spectrometric (FAAS) determinations. In this method a newly synthesized organic coprecipitant, 5-chloro-3-[4-(trifluoromethoxy) phenylimino]indolin-2-one (CFMEPI), was used without adding any carrier element for coprecipitation of chromium(III). After reduction of chromium(VI) by concentrated H(2)SO(4) and ethanol, the procedure was applied for the determination of total chromium. Chromium(VI) was calculated as the difference between the amount of total chromium and chromium(III). The optimum conditions for coprecipitation and speciation processes were investigated on several commonly tested experimental parameters, such as pH of the solution, amount of coprecipitant, sample volume, etc. No considerable interference was observed from the other investigated anions and cations, which may be found in natural water samples. The preconcentration factor was found to be 40. The detection limit for chromium(III) corresponding to three times the standard deviation of the blank (N = 10) was found 0.7 mu g L(-1). The present procedure was successfully applied for speciation of chromium in several liquid and solid environmental samples. In order to support the accuracy of the method, the certified reference materials (CRM-TMDW-500 Drinking Water and CRM-SA-C Sandy Soil C) were analyzed, and standard APDC-MIBK liquid-liquid extraction method was performed. The results obtained were in good agreement with the certified values. (C) 2008 Elsevier B.V. All rights reserved.