Untargeted and Targeted Discrimination of Honey Collected by Apis cerana and Apis mellifera Based on Volatiles Using HS-GC-IMS and HS-SPME-GC-MS.

Fraudulent acts regarding honey authenticity that use Apis mellifera honey as a substitute for Apis cerana honey have garnered considerable concern in China and triggered a trust crisis from consumers. In this study, untargeted metabolomics analysis was carried out based on volatile fractions in honey from A. cerana and A. mellifera using headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS). Honey from A. cerana and A. mellifera was discriminated by HS-GC-IMS profiling, principal component analysis, and orthogonal partial least-squares discrimination analysis. Tentative markers were identified from p-values and the variable importance in projection analysis and confirmed using the retention index, mass fragments, and reference standards by gas chromatography-mass spectrometry (GC-MS). A targeted method was established using the headspace solid phase coupled with microextraction GC-MS (HS-SPME-GC-MS) to quantitate the markers. The results demonstrated that the developed untargeted and targeted metabolomics approach performed well when discriminating honey from A. cerana and A. mellifera.