A method is presented and described for speciation, extraction and preconcentration of Cr(III)and Cr(VI) based on dynamic and static solid phase extraction techniques. Three newly designed alumina phases-physically adsorbwd-isatin-thiosemicarbazone (I-III) were synthesized, characterized, tested for stability and applied as inorganic ion exchangers and chelating, solid sorbents for various metal ions. The selectivity characteristics incorporated into these alumina phases were studied and evaluated via determination of the distribution coefficients and separation factors of chromium species versus other interacting metal ions. Quantitative recovery of Cr(VI) was accomplished by alumina phases (I-III) in pH 1.0 giving percentage extraction values of similar to 99.9-100.0%, while Cr(III) was found to he quantitatively recovered by these sorbents in pH 7.0 leading to percentage extraction values similar to 100.0% with minimal or no interference between these two species under the Studied buffering conditions. Selective solid phase speciation and preconcentration of Cr(III) and Cr(VI) in various real water samples were Successfully performed and accomplished by newly designed alumina phases (I-III) via a preconcentration micro-column. (C) 2008 Elsevier B.V. All rights reserved.