Four-stage (low-)flow modulation comprehensive gas chromatography–quadrupole mass spectrometry for the determination of recently-highlighted cosmetic allergens

• A flow-modulated GC × GC–MS method has been developed for perfume allergen analysis.
• MS-compatible gas flows were used.
• The 54 allergens indicated by the SCCS were subjected to GC × GC–MS determination.
• Allergen quantification was performed by using extracted-ions.

The present research is based on the development and use of a flow-modulation (FM) comprehensive two-dimensional gas chromatography–quadrupole mass spectrometry (GC × GC–qMS) method for the determination of recently-highlighted (by the Scientific Committee on Consumer Safety) fragrance allergens (54) in cosmetics. FM GC × GC–qMS conditions were finely tuned to generate flow conditions (≈7 mL min−1) compatible with the qMS system used. Six-point calibration curves, over the range 1, 5, 10, 20, 50, 100 mg L−1, were constructed for the 54 target allergens, with satisfactory linearity observed in all cases. Absolute quantification was performed by using extracted ions; target analyte identification was performed through measurement of ion ratios (qualifier/quantifier), full-scan MS database matching and the use of linear retention indices. Additional analytical figures of merit subjected to measurement were intra-day repeatability, accuracy at the 25 and 5 mg L−1 levels, and limits of detection and quantification. The number of data points per peak, along with mass spectral skewing, was also subjected to evaluation. Finally, the FM GC × GC–qMS method was used not only for the quantification of target allergens in five commercial perfumes, but also for general qualitative profiling.