Fast screening of perfluorooctane sulfonate in water using vortex-assisted liquid–liquid microextraction coupled to liquid chromatography–mass spectrometry

Abstract

Fast screening of trace amounts of the perfluorooctane sulfonate anion (PFOS) in water samples was performed following a simple, fast and efficient sample preparation procedure based on vortex-assisted liquid–liquid microextraction (VALLME) prior to liquid chromatography–mass spectrometry. VALLME initially uses vortex agitation, a mild emulsification procedure to disperse microvolumes of octanol, a low density extractant solvent, in the aqueous sample. Microextraction under equilibrium conditions is thus achieved within few minutes. Subsequently, centrifugation separates the two phases and restores the initial microdrop shape of the octanol acceptor phase, which can be collected and used for liquid chromatography–single quadrupole mass spectrometry analysis. Several experimental parameters were controlled and the optimum conditions found were: 50 μL of octanol as the extractant phase; 20 mL aqueous donor samples (pH = 2); a 2 min vortex extraction time with the vortex agitator set at a 2500 rpm rotational speed; no ionic strength adjustment. Centrifugation for 2 min at 3500 rpm yielded separation of the two phases throughout this study. Enhanced extraction efficiencies were observed at low pH which was likely due to enhanced electrostatic interaction between the negatively PFOS molecules and the positively charged octanol/water interface. The effect of pH was reduced in the presence of sodium chloride, likely due to electrical double layer compression. The linear response range for PFOS was from 5 to 500 ng L −1 (coefficient of determination, r 2, 0.997) and the relative standard deviation for aqueous solutions containing 10 and 500 ng L −1 PFOS were 7.4% and 6.5%, respectively. The limit of detection was 1.6 ng L −1 with an enrichment factor of approximately 250. Analysis of spiked tap, river and well water samples revealed that matrix did not affect extraction.