Flower scenting is an effective way to enhance the aroma of green tea (GT), including those osmanthus scented green tea (OSGT). However, the mechanism of aroma enhancement by scenting is still unclear. Here, the volatiles of GT, OSGT, and osmanthus were detected by GC–MS. The total volatile content of OSGT was significantly increased compared to GT, with the flowery and coconut aromas enhanced. Furthermore, 17 of 139 volatiles were responsible for the enhancement by GC–olfactometry and their absolute odor activity values (OAVs). Aroma recombination, omission and addition experiments showed that dihydro-β-ionone, (E)-β-ionone, (E, E)-2,4-heptadienal, geraniol, linalool, α-ionone, and γ-decalactone were the key aroma volatiles with flowery or coconut aromas. Additionally, the dynamics of the key volatiles (OAVs >1) from different scenting durations were analyzed, proving that the optimal duration was 6–12 h. This study provides new insight into the mechanism of aroma formation during OSGT production.
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