Enantiomeric separation and precise quantification of chiral volatiles in Wuyi rock teas using an efficient enantioselective GC × GC-TOFMS approach.

[Display omitted] • A novel Es-GC×GC-TOFMS approach to separate chiral volatiles in tea was established. • Volatile enantiomers in Wuyi rock teas from four cultivars were firstly quantitated. • Limits of quantitation of linalool oxides A−B in teas were as low as 0.2 pg/mL. • R -α-Ionone, S -(E)-nerolidol etc. were the potential markers to distinguish cultivar. • 7 Volatile enantiomers were identified as aroma-active compounds in Wuyi rock teas. Chiral volatiles play important roles in the formation of aroma quality of foods. To date, enantiomeric characteristics of chiral volatiles in Wuyi rock tea (WRT) and their aroma contributions are still unclear. In this study, an efficient enantioselective comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (Es-GC × GC-TOFMS) approach to separate and precisely quantitate 24 pairs of chiral volatiles in WRTs was established, and the enantiomeric distribution and aroma contribution of chiral volatiles among WRTs from four representative cultivars were investigated. Enantiomeric ratio (ER) of R -α-ionone (80%) in Dahongpao (DHP), ER of S -α-terpineol (57%) in Jinfo (JF), ERs of R -γ-heptanolactone (69%), S -γ-nonanolactone (55%), (2 R , 5 S)-theaspirane B (91%), concentration of S -(E)-nerolidol (313.37 ng/mL) in Rougui (RG) and concentration of R -α-ionone (33.01 ng/mL) in Shuixian (SX) were unique from other types of WRTs, which were considered as the potential chemical markers to distinguish WRT cultivars. The OAV assessment determined 7 volatile enantiomers as the aroma-active compounds, especially R -α-ionone and R -δ-octanolactone in SX, as well as S -(E)-nerolidol and (1 R , 2 R)-methyl jasmonate in RG contribute much to aroma formation of the corresponding WRTs. The above results provide scientific references for discrimination of tea cultivars and directed improvement of the aroma quality of WRT. [ABSTRACT FROM AUTHOR]