As a semifermented tea, oolong is exceedingly popular worldwide for its elegant, flowery aroma and mellow, rich taste. However, recent marketing trends for old oolong teas and their chemical quality largely remain unexplored. In this study, we applied widely targeted metabolomics using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) combined with multivariate analysis to investigate the chemical change of oolong teas in the aging process. With the increasing of store time, most nongalloylated catechins; tannins, including TFs and proanthocyanidins; flavonols and glycosylated flavonols; amino acids and their derivatives; nucleotides and their derivatives; and lots of alkaloids and phospholipids declined, while most fatty acids and organic acids increased, and galloylated catechins, GA, and caffeine were almost stable. The result also suggested that approximately seven years (but not an infinite extension) was a special period for oolong tea storage, which brings about excellent taste.

An aroma-based method for distinguishing different grades of Nongxiang Tieguanyin was explored by taking special grade (K110) and 1–4 grades (K101, K102, K103, and K104) of this tea as samples. Tea samples were analyzed by gas chromatography–mass spectrometry (GC-MS) combined with chemometrics. Results showed differences in the types and relative contents of aroma components among different grades of Nongxiang Tieguanyin tea. In the principal component analysis (PCA) scoring plot, except for K102 and K103, tea samples of different grades were distributed in different regions. Components satisfying variable important for the projection (VIP) > 1 and peak areas with significant differences (p < 0.05) among different tea grades were screened. Finally, 18 differential variables were screened out from 143 volatiles. The clustering results of these variables were consistent with those of PCA. K102 and K103 were initially clustered into one group and then clustered with K101, K110, and K104 in turn. The clear PCA separation of these samples and uniform hierarchical cluster analysis (HCA) clustering results suggests that GC-MS coupled with chemometrics analysis is a valid and accurate approach for discriminating different grades of Nongxiang Tieguanyin. The screened differential variables could represent a difference in aroma quality among five grades of Nongxiang Tieguanyin tea. Clear rules between peak area and the grade were also observed in some differential variables. 1-Ethylpyrrole and unknown-32 were positively correlated with grade. 2-Methylfuran, 2-ethylfuran, 2-methylidenecyclopentan-1-ol, mesityl oxide, 2-amylfuran, and D-limonene were negatively correlated with grade. The peak areas of methyl acetate, dimethyl sulfide, 6-methylhept-5-en-2-one, and (Z)-β-ocimene initially decreased but then increased with declining grade. The toluene content was especially high in K104 but only a negligible difference was observed among other grades. This study provides a potential method for differentiating Nongxiang Tieguanyin teas of different grades based on aroma. Unknown samples could be classified by comparison of their spatial distribution with those of known standard samples in PCA or HCA, as well as the peak area differences of differential variables between unknown samples and known standard samples.

Fatty acids (FAs) are important precursors of oolong tea volatile substances, and their famous derivatives have been shown to be the key aroma components. However, the relationship between fatty acids and their derivatives during oolong tea production remains unclear. In this study, fresh Tieguanyin leaves were manufactured into oolong tea and green tea (control), and fatty acids and fatty acid-derived volatiles (FADV) were extracted from processed samples by the sulfuric acid–methanol method and solvent-assisted flavor evaporation (SAFE), respectively. The results showed that unsaturated fatty acids were more abundant than saturated fatty acids in fresh leaves and decreased significantly during tea making. Relative to that in green tea, fatty acids showed larger variations in oolong tea, especially at the green-making stage. Unlike fatty acids, the FADV content first increased and then decreased. During oolong tea manufacture, FADV contents were significantly and negatively correlated with total fatty acids; during the green-making stage, methyl jasmonate (MeJA) content was significantly and negatively correlated with abundant fatty acids except steric acid. Our data suggest that the aroma quality of oolong tea can be improved by manipulating fatty acid transformation.

Characteristic aroma is a well-appreciated feature contributing to tea quality. Although extensive studies have been made to investigate aroma biosynthesis and gene expressions during tea making processes, it remains unclear whether the endogenous volatile biosynthesis during postharvest tea processing contributes to the aroma quality of made tea. To critically evaluate this question, we used the same batch of fresh tea leaves and produced three different types of tea with different degrees of fermentation (green tea, oolong tea, and black tea). Total volatiles were extracted by solvent-assisted-flavor evaporation, then quantified by gas chromatography-flame ionization detector combined with response factor correction for quantitative measurement. Compared with fresh tea leaves, the volatile profiles of the made teas were dramatically altered, with significant loss for the majority of endogenous volatiles and simultaneous gain for non-endogenous volatiles. By calculation of odor-activity values, the potential volatiles contributing to the aroma characteristics of each tea type were identified. Our data suggest that postharvest synthesis of endogenous volatiles did not contribute to the aroma quality of made tea.