The toxicity of aluminium towards organisms of terrestrial [1,2] and aquatic [3,4] habitats depends primarily on its specific forms. Labile positively charged monomeric forms of aluminium (Al 3+ , Al(OH) 2+ and Al(OH) 2 + ) have been recognised as the most toxic aluminium species [1][2][3][4][5]. Therefore, investigations were directed to the development of analytical methods which enable determination not only of the sum of positively charged monomeric aluminium species [6][7][8][9][10][11][12][13][14][15][16][17] but also allow distinction between particular aluminium forms [18][19][20][21][22][23][24][25][26][27]. In recent years ion chromatography in combination with post-column derivatization using UV-VIS [18,19] or fluorescence detection [20,21] were frequently employed for speciation of cationic aluminium complexes. Fluoro-, oxalato-, and citrato-aluminium species were identified by distinct peaks and separated from sulphato-aluminium which was eluted at the retention time of Abstract. Cation-exchange fast protein liquid chromatography -electrothermal atomic absorption spectrometry (FPLC -ETAAS) was applied for the speciation of trace amounts of aluminium. An aqueous 8 mol dm -3 NH 4 NO 3 linear gradient elution in 10 minutes enabled separation of positively charged monomeric aluminium species in aqueous solution. Separated aluminium species were collected in 0.5 cm 3 fractions and aluminium determined "off line" after fourfold dilution by ETAAS. The ability of NH 4 NO 3 to completely decompose at low temperature in the graphite tube during the ashing step enabled quantitative and reproducible determination of aluminium. After applying Chelex-100 resin in a cleaning procedure of the eluent, the eluent blank was very low (< 1.0 ng cm -3 Al). When 1 cm 3 of sample was injected on the column resin, the limit of detection (3 s) for the separated aluminium species determined by ETAAS was found to be 3 ng cm -3 . Good repeatability of measurement of separated aluminium species (relative standard deviation ±5%) was obtained under the recommended analytical conditions. The influence of some inorganic and organic complexing ligands at pH values of 4.0 and 6.0 on the speciation of aluminium was also investigated. The method developed was successfully applied for the speciation of aluminium in soil extracts and natural water samples at ng cm -3 levels.Key words. Speciation of trace amounts of aluminium − fast protein liquid chromatography-electrothermal atomic absorption spectrometry − soil extracts − natural waters.