Study on dynamic alterations of volatile organic compounds reveals aroma development over enzymatic-catalyzed process of Tieguanyin oolong tea production

• The first on metabolic profile and formation mechanism of Tieguanyin aroma. • Multi-stress occurred over ECP stage induced the alterations of VOCs. • The dynamic proportion between floral-fruity/green leaf volatiles was revealed. To elucidate the formation of characteristic aroma over enzymatic-catalyzed processes (ECP), GC–MS-based volatile-metabolomic combined with desorption-electrospray-ionization coupled mass-spectrometry-imaging (DESI-MSI) were employed to analyze the changes of volatile organic compounds (VOCs) in Tieguanyin tea. A total of 579 VOCs were obtained, from which 24 components involved in five pathways were identified as biomarkers. Among these, four VOCs including 2-furancarboxylic acid, 4-methylbenzaldehyde, N-benzylformamide, cuminaldehyde, were detected in both DESI-MSI and GC–MS analysis, exhibiting dynamic changes along processing steps. RNA-sequencing analysis indicated the genes referring to stress response were activated during tea processing, facilitating the accumulation of flora-fruity aroma in tea leaf. Metabolic pathways analysis revealed that the increase in floral-fruity related components such as volatile terpenoids, phenylpropanoids/benzenoids, indole, alongside a decrease in green leaf volatiles including ( E )-2-Hexenal, ( Z )-3-Hexenol, played a crucial role in development of characteristic aroma, which could be a feasible index for evaluating processing techniques or quality of oolong tea.