Multidimensional Analysis Reveals the Flavor Quality Formation Mechanism During the Primary Pile Fermentation of Dark Tea

Pile fermentation is a crucial process for developing the characteristic mellow taste and aged aroma of dark tea, yet the internal quality transformation mechanism of this process is still unclear. This study employed a high-sensitivity analytical platform based on gas chromatography–mass spectrometry (GC-MS) to systematically investigate the dynamic interplay between key chemical components, enzyme activities, and volatile compounds during the pile fermentation of primary dark tea. Our findings revealed a significant decrease in ester-type catechins, crude protein, and protopectin, alongside a notable accumulation of non-ester-type catechins, gallic acid, and soluble components. The multi-enzyme system—comprising PPO/POD, pectinase/cellulase, and protease—cooperatively drove the oxidation of phenols, cell wall degradation, and the release of aromatic precursors. This was complemented by GC-MS analysis, which identified and quantified 103 volatile compounds across nine chemical classes. The total content of volatile compounds increased significantly, with alcohols, esters, and aldehydes/ketones being the dominant groups. Floral and fruity compounds such as linalool and geraniol accumulated continuously, while esters exhibited an initial increase followed by a decrease. Notably, carotenoid degradation products, including β-ionone, were significantly enriched during the later stages. This study revealed a “oxidation–hydrolysis–reconstruction” metabolic mechanism co-driven by microbial activity and a multi-enzyme system, providing a theoretical foundation for the precise regulation of pile fermentation and targeted quality improvement of primary dark tea.