Abstract:

The gas chromatography-mass spectrometric (GC-MS) method with two different ionization techniques, electron impact (EI) and positive chemical ionization (PCI), have been developed for the simultaneous determination of three sterenes in olive oil. The olive oil sample was dissolved in petroleum ether, followed by cleanup on a silica gel column and finally analyzed by GC-EI/MS and GC-PCI/MS in selected ion monitoring mode. The quantitation was performed by internal standard calibration with cholesta-3, 5-diene as internal standard. These two methods were compared in terms of linearity, accuracy, precision and sensitivity. Good linearities were obtained with correlation coefficients (r) higher than 0.999 for campesta-3, 5-diene in the range of 0.024 to 0.48 mg/L, stigmasta-3, 5, 22-triene in the range of 0.02 to 0.50 mg/L and stigmasta-3, 5-diene in the range of 0.03 to 0.75 mg/L. The accuracy test was carried out at three spiked levels in extra virgin olive oil. The average recoveries ranged from 88.7% to 99.5% (EI) and 87.1% to 109.2% (PCI), with relative standard deviations (RSDs, n=6) not higher than 8.3%. Limits of quantification (LOQs, S/N=10) were 0.03 mg/kg (EI) and 0.03-0.10 mg/kg (PCI). Comparative analysis showed a large number of fragment ions could be obtained in EI mode while quasi-molecular ions or other adduct molecular ions were the most abundant ion formed in the PCI mode. Besides, PCI has a better selectivity than EI when applied to real samples. In conclusion, these two ionization techniques are complementary and alternative in the routine analysis of sterenes in olive oil.

Key words: electron impact ionization (EI), gas chromatography-mass spectrometry (GC-MS), positive chemical ionization (PCI), sterenes