Speciation of Cr(III)/Cr(VI) from water using olive pomace (OP) was improved by partial pyrolysis of OP. The sorbents were characterized by physicochemical techniques. Sorption of Cr(III) on raw and partially pyrolyzed OP sorbents followed Freundlich isotherm and second-order rate kinetics. OP pyrolyzed at 150 degrees C (sorbent OP-150) exhibited maximum sorption capacity, favorability and the lowest sorption energy. Sorption was exothermic and spontaneous for the raw-OP and OP pyrolyzed at 100 or 150 degrees C; but endothermic and non-spontaneous for OP pyrolyzed at 200, 250, 300 or 400 degrees C. A speciation method of chromium was proposed, in which Cr(III) was selectively retained at pH 3 on sorbent OP-150: while total Cr was determined after reduction of Cr(VI). The method was selective with a detection limit for Cr(III) of 1.58 mu L(-1). The method was applied on natural and industrial waters (recoveries >97.7%, RSD's <9%) and on tobacco leaves certified reference material (INCT-PVTL-6). (C) 2011 Elsevier Ltd. All rights reserved.