Determination of perfluorinated carboxylic acids in fish fillet by micro-solid phase extraction, followed by liquid chromatography–triple quadrupole mass spectrometry

• Ten PFCAs were determined simultaneously using μ-SPE in fish fillet.
• The effect of the matrix on MS signals was evaluated.
• Surfactant-incorporated ordered mesoporous silica was applied as sorbent.
• Recoveries ranged from 77% to 120%, and were independent of concentration.

In the current study, a simple, fast and efficient combination of protein precipitation and micro-solid phase extraction (μ-SPE) followed by liquid chromatography–triple quadrupole tandem mass spectrometry (LC–MS/MS) was developed for the determination of perfluorinated carboxylic acids (PFCAs) in fish fillet. Ten PFCAs with different hydrocarbon chain lengths (C5–C14) were analysed simultaneously using this method. Protein precipitation by acetonitrile and μ-SPE by surfactant-incorporated ordered mesoporous silica were applied to the extraction and concentration of the PFCAs as well as for removal of interferences. Determination of the PFCAs was carried out by LC–MS/MS in negative electrospray ionization mode. MS/MS parameters were optimized for multiple reaction monitoring of the analytes. 13C mass labelled PFOA as a stable-isotopic internal standard, was used for calibration. The detection limits of the method ranged from 0.97 ng/g to 2.7 ng/g, with a relative standard deviation of between 5.4 and 13.5. The recoveries were evaluated for each analyte and were ranged from 77% to 120%. The t-test at 95% confidence level showed that for all the analytes, the relative recoveries did not depend on their concentrations in the explored concentration range. The effect of the matrix on MS signals (suppression or enhancement) was also evaluated. Contamination at low levels was detected for some analytes in the fish samples. The protective role of the polypropylene membrane used in μ-SPE in the elimination of matrix effects was evaluated by parallel experiments in classical dispersive solid phase extraction. The results evidently showed that the polypropylene membrane was significantly effective in reducing matrix effects.