GC–MS and LC-MS/MS metabolomics revealed dynamic changes of volatile and non-volatile compounds during withering process of black tea

High-performance liquid chromatography (HPLC), headspace solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC–MS) and ultra-high performance liquid chromatography–Q-Exactive HF-X mass spectrometer (UHPLC–Q-Exactive HF/MS) were carried out to reveal dynamic changes of volatile and non-volatile compounds during the withering process of black tea. A total of 118 volatile organic compounds (VOCs) and 648 metabolites were identified in fresh and withered tea-leaves, respectively. Among them, 47 VOCs (OAV > 1.0) for the aroma formation, and 46 characteristic metabolites (VIP > 1.50, p < 0.01) selected through orthonormal partial least squares-discriminant analysis, indicated the withering contribution during black tea processing. Overall, the withering promoted alcohols, aldehydes, phenols, heterocyclic oxygen, hydrocarbons and halogenated hydrocarbons through relevant hydrolyzation, decomposition, terpene synthesis, and O-methylation. The hydrolyzation, O-methylation, condensation and N-acylation of kaempferol glycosides, quercetin glycosides, ester catechins, and gallic acid generated the accumulation of methoxyl flavonoids and flavonoid glucosides, dihydrokaempferol, syringic acid, theaflavins, and N-acylated amino acids, respectively.