Baijiu is a traditional Chinese spirit with an extraordinarily rich pattern of volatile compounds resulting from the microflora involved in fermentation, as well as the complexity of technological process. Comprehensive two-dimensional gas chromatography in the conventional and reversed column setups (non-polar – polar and polar – non-polar columns) was tested for its ability to differentiate Baijiu samples in terms of their aroma and origin (region). A total of 65 Baijiu samples were used for the study and volatile compounds were extracted by SPME with a subsequent analysis by GC×GC-TOFMS. Orthogonality of both setups was compared, so was the number of compounds identified using each setup. Repeatability of compound groups for the conventional and reversed column setups was compared; moreover, multiblock orthogonal component analysis (MOCA) was used to visualize data sets. OPLS-DA was used for Baijiu classification. Both column setups provided excellent discrimination of the Light, Soy sauce, Feng and Herbal aromas. A better classification result for the Strong and Jian aromas was recorded for the conventional column setup. Within the Strong aroma using OPLS-DA both column setups provided perfect abilities to discriminate Baijiu from the Sichuan, Heilongjiang and Jiangsu regions. Two validation methods were applied in the classification models - all the predictive abilities evaluated by the internal validation were further confirmed by the external validation.

白酒是中华民族的传统精神，由于发酵中的菌群以及工艺过程的复杂性，挥发性化合物的形式异常丰富。测试了常规和反向色谱柱设置（非极性-极性和极性-非极性的色谱柱）中全面二维气相色谱法在区分白酒样品的香气和来源（区域）方面的能力。总共使用了65个白酒样品进行研究，并通过SPME提取了挥发性化合物，随后通过GC×GC-TOFMS进行了分析。比较了两种设置的正交性，因此比较了使用每种设置识别出的化合物数量。比较了常规和反向色谱柱设置中化合物组的可重复性；此外，多块正交分量分析（MOCA）用于可视化数据集。OPLS-DA用于白酒分类。两种色谱柱设置都能很好地区分清淡，酱油，枫香和草本香气。对于常规色谱柱设置，记录到的浓香和Jian香的分类结果更好。在使用OPLS-DA的强烈香气中，两种色谱柱设置都提供了区分白酒与四川，黑龙江和江苏地区的完美能力。在分类模型中应用了两种验证方法-内部验证评估的所有预测能力均由外部验证进一步确认。对于常规色谱柱设置，记录到的浓香和Jian香的分类结果更好。在使用OPLS-DA的强烈香气中，两种色谱柱设置都提供了区分白酒与四川，黑龙江和江苏地区的完美能力。在分类模型中应用了两种验证方法-内部验证评估的所有预测能力均由外部验证进一步确认。对于常规色谱柱设置，记录到的浓香和Jian香的分类结果更好。在使用OPLS-DA的强烈香气中，两种色谱柱设置都提供了区分白酒与四川，黑龙江和江苏地区的完美能力。在分类模型中应用了两种验证方法-内部验证评估的所有预测能力均由外部验证进一步确认。