Hemimicelles and admicelles of sodium dodecyl sulfate (SDS) on alumina and cetyltrimethyl ammonium bromide (CTAB) on silica were evaluated for the concentration and purification of the priority estrogens estrone (E1), 17β-estradiol (E2) and ethynylestradiol (EE2) from sewage and river samples. Retention was based on analyteâ sorbent hydrophobic and cationâ Ï interactions. Parameters affecting the SPE of estrogens on both types of sorbents were comparatively investigated. Adsolubilization was quantitative for SDS hemimicelles/admicelles and CTAB admicelles. SDS hemimicelle-coated alumina was the sorbent selected on the basis of the lower elution volume required and the higher sample flow rate allowed. Combination of estrogen adsolubilization-based SPE with liquid chromatography-diode array/fluorescence detection permitted the quantification of the target compounds with detection limits ranging from 20 to 100 ng l^{â 1}. The relative standard deviation ranged from 3 to 8%. The approach developed was applied to the determination of estrogens in raw and treated sewage and river samples. The recovery found for estrogens in these environmental matrices was between 85 and 105%.