Ion-pair solid-phase extractive derivatization of 4-alkylphenols with pentafluoropyridine for gas chromatography–mass spectrometry

The ion-pair solid-phase extraction (SPE) of 4-alkylphenols followed by derivatization with pentafluoropyridine is demonstrated. Under alkaline conditions, the 4-alkylphenols could be efficiently adsorbed on a C18 SPE cartridge conditioned with an ion-pair reagent, tetra-n-hexylammonium bromide. The ion pairs, ammonium phenolates, formed on the C18 solid phase, were eluted with a solvent containing the derivatizing reagent, pentafluoropyridine, and completely derivatized during the elution. After optimization of the adsorption and derivatization, we established a method for the determination of the 4-alkylphenols in water samples. The method showed good linearity between 20 and 1000 ng (200–10,000 ng for nonylphenol). By processing 20-ml samples, the method detection limits (MDL) were in the range of 5.2–8.9 ng/l for the 4-alkylphenols (76 ng/l for nonylphenol). To evaluate its applicability to a real aqueous matrix, several river water samples were analyzed.