Beijing rice vinegar is a typically traditional Chinese cereal vinegar and prevalent in the northern part of China. In this study, the volatile aroma analysis of different fermentation stages of Beijing rice vinegar was carried out by headspace-solid phase micro-extraction coupled with gas chromatography mass spectrometry (FIS-SPME-GC-MS). The aroma could be classified into acids, alcohols, esters, aldehydes, ketones, polyphenols and heterocyclic compounds. The aroma constituents varied at each fermentation stage. Principle component analysis (PCA) was employed to distinguish the specific aroma compounds. At the alcoholization stage, alcohols were mainly ethanol (1993.10 mu g/100 mL, 70%), and phenyl-ethyl alcohol (588.64 mu g/100 mL, 20%). The ethyl ester meanwhile started to be produced and was the most prevalent ester. The high contents of ethanol, 3-methyl-butanol and phenyl-ethyl alcohol could be the potential aroma biomarker for the alcoholization stage. At the vinegarization stage, ethanol was largely consumed, as well as i-butanol and i-amyl alcohol. The concentration of volatile acids was 1948.01 mu g/100 mL with acetic acid the most dominant one ( > 90%). Acetic acid and 3-hydroxy-2-butanone were representative compounds for vinegarization stage and could be the potential biomarkers. Furthermore, the aroma comparison of 7 kinds of classic cereal vinegars was carried out. PCA results indicated that the specification of aroma biomarkers for each type of vinegar was practical, serving as the indicators or predictors for both the vinegar fermentation stage identification, vinegar sensory evaluation, and offering a potential for vinegar identification and quality improvement. The assessment strategy was also used to compare the typical Chinese and other important western vinegars.
