a b s t r a c tA new methodology has been developed for the determination of secondary alkane sulfonates (SAS), an anionic surfactant, in environmental matrices. Sediment and sludge samples were extracted using pressurized liquid extraction and sonication, whereas wastewater and surface water samples were processed using solid-phase extraction. Extraction recoveries were acceptable for both aqueous (78e120%) and solid samples (83e100%). Determination of SAS was carried out by high or ultra performance liquid chromatography e mass spectrometry using ion trap and time-of-flight detectors. The methodology was applied to samples from Guadalete River (SW Spain), where SAS concentrations below 1 mg L À1 were measured in surface water, and from 72 to 9737 mg kg À1 in sediments. Differential partitioning was observed for SAS homologues as those having a longer hydrocarbon chain which preferentially sorbed onto particulate matter. A preliminary environmental risk assessment also showed that SAS measured levels were not harmful to the aquatic community in the sampling area.