A sensitive solid-phase extraction technique (SPE) for the enrichment of Fe(III), Co(II), Mn(II) and Cr(III) prior to atomic absorption spectrometric analysis is described. Escherichia coli immobilized on Amberlite XAD-4 was used as a solid-phase extractor. The effects of the pH, amount of solid-phase, eluent type and volume of the sample solution on the recovery of the metal ions were investigated. The effect of diverse ions was also investigated. The recoveries of Fe(III), Co(II), Mn(II) and Cr(III) under the optimum conditions were found to be 99 +/- 2, 99 +/- 3, 98 +/- 2, 98 +/- 3%, respectively, at the 95% confidence level. The detection limits of the metal ions were found as to be 2.4, 3.8, 1.3 and 1.7 ng ml(-1) for Fe(III), Co(II), Mn(II) and Cr(III) respectively, by applying a preconcentration factor of 25. The proposed enrichment method was applied to the determination of analytes in Ataturk Dam water samples, and alloy samples (RSD < 5%). The accuracy of the method was verified on certified alloy samples (NBS SRM 85b and NBS SRM 59a). The analytes were determined with a relative error lower than 5% in water and alloy samples.