Additional file 1: Table S1. The content of TMPZ in RV and WV. Table S2. The peak area and the relative peak area value of four potential biomarkers in different aging period. Table S3. The levels and factors investigated in BBD. Figure S1. HPLC chromatogram of TMPZ. Figure S2. The results of bioactivity screening. Figure S3. Diagnostic efficacy evaluation using ROC curves of the four potential biomarker metabolites in two different vinegar. Figure S4. Trends of time-series analysis graphs of four potential biomarkers. (A) TMPZ (MAPE: 2.05853, MAD: 1.67627, fitted curve: Yt = 60.81+5.089xt); (B) Dihydroergotamine (MAPE: 1.63096, MAD: 0.15345, fitted curve: Yt = 6.726+0.7121xt); (C) Harmine (MAPE: 1.72704, MAD: 0.01711, fitted curve: Yt = 0.7764+0.05780xt); (D) 1,2,3,4-tetrahydroharmine (MAPE: 3.76071, MAD: 0.04998, fitted curve: Yt = 0.9695+0.0910xt). Figure S5. Response surfaces estimated from the full factorial design for the content of total alkaloids