A speciation procedure for Cr(III) and Cr(VI) based on column solid phase extraction on Amberlite XAD-2010 and flame atomic absorption spectrometry combination. Cr(VI) was quantitatively recovered on Amberlite XAD-2010 resin at pH range of 2.0-3.0 as its diethyldithiocarbamate complex, while the recoveries of Cr(III) was below 5%. The influences of the various parameters including amounts of the reagents, eluent type and its volume, sample volume, etc., on the quantitative recoveries were examined. The interference of matrix and coexistent elements for method were studied. The detection limit (corresponding to three times the standard deviation of the blank) and the enrichment factor for Cr(VI) were found to be 1.28 mu g/L and 25, respectively. To verify the accuracy of the method, drinking water certified reference material (CRM-TMDW-500) was analyzed and the results obtained were in good agreement with the certified value. The proposed method has been successfully applied to the speciation of Cr(III) and Cr(VI) in water samples and preconcentration of total chromium in environmental samples. (C) 2006 Elsevier B.V. All rights reserved.