Analysis of Allergens in Fragrance Samples Using a Comprehensive GCxGC in Combination with a High-Resolution Mass Spectrometry

Importance of the Topic

Fragrance formulations comprise hundreds of structurally similar natural and synthetic components. Traditional one-dimensional GC separations often fail to resolve coeluting compounds, hindering reliable identification and quantitation of allergenic constituents. High-resolution analysis of allergens in fragrances is essential for regulatory compliance, consumer safety, and quality assurance in cosmetic and personal care industries.

Objectives and Study Overview

This study aimed to demonstrate the power of comprehensive two-dimensional gas chromatography (GC×GC) coupled with high-resolution mass spectrometry (HRMS) to achieve confident identification and accurate quantitation of 64 fragrance allergens. An additional goal was to perform non-targeted profiling of different aroma classes and differentiate floral versus woody scent types through statistical analysis.

Methodology and Instrumentation

A GC×GC method using a reverse-flow modulator (RFM) was optimized to separate allergen standards and complex fragrance mixtures. Key instrumental details:

• GC system: Agilent 8890 GC with DB-1ms (20 m × 0.1 mm × 0.1 µm) 1D column and DB-17ms (5 m × 0.25 mm × 0.15 µm) 2D column
• Modulator: Reverse flow with 6.3 s modulation period, 0.5 min delay
• Detectors: Agilent 7250 GC/Q-TOF at 50 Hz data rate and flame ionization detector (FID)
• Carrier gas: Helium, 0.2 mL/min (1D) and 10 mL/min (2D) to FID, 1.3 mL/min split to MS
• Software: MassHunter Quantitative Analysis 12.1, GC Image 2024 R3, Mass Profiler Professional 15.1

Main Results and Discussion

All 64 allergen standards were baseline-resolved in GC×GC space, enabling precise integration and quantitation down to 1 ppm. Spiked fragrance samples (10 ppm and 100 ppm) showed accurate recovery across analytes using internal standards (1,4-dibromobenzene, 4,4′-dibromobiphenyl). Non-targeted profiling identified over 240 compounds, and multivariate analysis (volcano plots) highlighted markers distinguishing floral from woody fragrances. Accurate mass and linear retention indices yielded high confidence in compound assignments.

Benefits and Practical Applications

Combining GC×GC with HRMS enhances separation power, identification confidence, and quantitation accuracy of trace allergens in complex matrices. The approach streamlines regulatory testing, supports product safety assessments, and enables comprehensive compositional profiling for fragrance development and quality control.

Future Trends and Potential Applications

Integration of GC×GC-HRMS data with advanced chemometric and machine learning tools will further accelerate non-targeted screening and pattern recognition in fragrance analysis. Emerging high-throughput modulator designs and miniaturized detectors may expand applications into on-site monitoring, exposomics, and environmental odor profiling.

Conclusion

The comprehensive GC×GC–HRMS workflow with a reverse-flow modulator delivers superior separation, accurate mass identification, and robust quantitation of allergens in fragrance samples. This platform provides a powerful solution for both targeted regulatory analyses and broad non-targeted compositional studies.

References

No formal literature references were cited in the original poster.