The capability of surfactant-coated mineral oxides to aid the solid-phase extraction (SPE) of amphiphiles based on the formation of mixed hemimicelles/admicelles was investigated. The approach is illustrated by studying the adsolubilization of benzalkonium homologue (C(12), C(14), C(16)) surfactants (BAS) on sodium dodecyl sulfate (SDS)-coated alumina. These oppositely charged surfactants form mixed aggregates on alumina causing retention of BAS by strong hydrophobic and ionic interactions. The recovery of BAS was found quantitative and independent of the alkyl chain length under a wide range of experimental conditions (3-200 mg of SDS/g of alumina; pH 2-11; sample flow rate 3-20 mL/min, and sample loading volume 0.025-1 L). Anionic and nonionic surfactants and electrolytes did not interfere to the levels found in raw sewage. Combination of BAS adsolubilization-based SPE with liquid chromatography/electrospray ionization in positive ion mode/ion trap mass spectrometry permitted the quantification of BAS with detection limits of 4 ng/L and their identification by isolation and subsequent fragmentation in the ion trap. The approach developed was applied to the determination of BAS in raw and treated sewage and river samples. The concentrations of benzalkonium surfactants found ranged between 0.1 and 49 microg/L.