Untargeted and Targeted Discrimination of Honey Collected by <i>Apis cerana</i> and <i>Apis mellifera</i> Based on Volatiles Using HS-GC-IMS and HS-SPME-GC–MS

Abstract

Fraudulent acts regarding honey authenticity that use <i>Apis mellifera</i> honey as a substitute for <i>Apis cerana</i> 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 <i>A. cerana</i> and <i>A. mellifera</i> using headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS). Honey from <i>A. cerana</i> and <i>A. mellifera</i> was discriminated by HS-GC-IMS profiling, principal component analysis, and orthogonal partial least-squares discrimination analysis. Tentative markers were identified from <i>p</i>-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 <i>A. cerana</i> and <i>A. mellifera</i>.