DOI:10.3969/j.issn.2095-6002.2019.05.007
中图分类号:TS262.3
老白干老五甑工艺和三排净工艺原酒的挥发性成分分析
樊倩1,2， 王新磊2,3， 郑福平1,2， 李贺贺1,2， 孙宝国1,2， 张煜行3， 张福艳3
| 【作者机构】 | 1北京工商大学食品质量与安全北京实验室； 2北京工商大学北京食品营养与人类健康高精尖创新中心； 3河北衡水老白干酒业股份有限公司 |
| 【分 类 号】 | TS262.3 |
| 【基 金】 | 国家重点研发计划项目(2016YFD0400500) |
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出版信息
老白干老五甑工艺和三排净工艺原酒的挥发性成分分析
白酒是中国的国酒，是世界六大蒸馏酒之一[1]。白酒中有98%的乙醇水溶液及2%的微量成分，微量成分的差异构成了不同白酒的独特香气与口感[2-3]。老白干香型白酒以衡水老白干白酒为代表，其香醇的口感、清雅的香气，深受消费者喜爱[4]。有研究采用气相色谱- 质谱联用(gas chromatography-mass spectrometry,GC-MS)结合气相色谱- 嗅闻(gas chromatography-olfactometry, GC-O)分析了老白干白酒，鉴定出了4-乙基愈创木酚、乙酸2-苯乙酯、丁酸、3-甲基丁醇、β-苯乙醇、2-乙酰基-5-甲基呋喃、苯丙酸乙酯、γ-壬内酯、3-甲基丁酸、香兰素、乙酸乙酯、1,1-二乙氧基-3-甲基丁烷和2,2-二乙氧基乙基苯等风味成分对香气贡献较大[5]。王敏等[6]采用顶空固相微萃取(head space solid phase microextraction, HS-SPME)和GC-MS在老白干香型白酒中分析鉴定出了101种香气成分，首次鉴定出大马士酮、里那醇。Du等[7]分析比较了HS-SPME不同萃取纤维提取老白干香型白酒的效率，结果显示50/30 μm DVB/CAR/PDMS萃取纤维较适合。
全二维气相色谱- 飞行时间质谱技术(comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry, GC×GC-TOF/MS)能够有效地解决一维GC-MS低灵敏度、低分辨率的问题[8-9]，更有利于挥发性风味化合物的分离鉴定。目前GC×GC-TOF/MS技术已经被用于对酱香型[10-11]、浓香型[12-13]、清香型[14]、芝麻香型[15]白酒中挥发性组分的分析，极大地提高了白酒的分析检测水平。白酒的不同酿制工艺对其风味口感会有一定的影响[16-17]，传统老白干香型白酒酿制工艺分为混蒸混烧老五甑和清蒸清烧三排净2种工艺[18-19]，其区别主要为混蒸混烧老五甑工艺是将发酵好的酒醅与高粱同时蒸料蒸酒，清蒸清烧三排净工艺是将酒醅与高粱分别蒸料和蒸酒，而对于这2种工艺酿制的白酒风味物质组成差异尚不清楚。为此，本研究采用HS-SPME结合GC×GC-TOF/MS技术分析比较2种不同工艺老白干香型白酒挥发性风味成分，研究结果为进一步探究不同酿制工艺对于老白干香型白酒风味形成机制提供理论依据。
1 材料与方法
1.1 材料与试剂
老白干香型混蒸混烧老五甑工艺原酒，发酵期24 d，酒精度68%；老白干香型清蒸清烧三排净工艺原酒，发酵期27 d，酒精度66%。样品均为河北衡水老白干酒业股份有限公司生产，原酒酒精度测定按照GB/T 10345—2007 白酒分析方法[20]，以酒精计测得。
氯化钠，分析纯，国药集团化学试剂有限公司。无水乙醇，色谱纯，上海阿拉丁生化科技股份有限公司。C6～C30正构烷烃混合物，丙酸辛酯，色谱纯，上海西格玛奥德里奇贸易有限公司。甲酸乙酯、乙酸乙酯、异丁酸乙酯、丙烯酸乙酯、乙酸异丁酯、丁酸乙酯、丙酸丙酯、2-甲基丁酸乙酯、甲酸异戊酯、异戊酸乙酯、异丁酸异丁酯、丁酸丙酯、乙酸异戊酯、戊酸乙酯、丙酸丁酯、己酸甲酯、己酸乙酯、乙酸己酯、己酸丙酯、乳酸乙酯、庚酸乙酯、己酸异丁酯、辛酸甲酯、辛酸乙酯、己酸异戊酯、乙酸辛酯、壬酸乙酯、辛酸异丁酯、乙酸壬酯、癸酸甲酯、己酸己酯、癸酸乙酯、苯甲酸乙酯、琥珀酸二乙酯、癸酸丙酯、十一酸乙酯、癸酸异丁酯、苯乙酸乙酯、水杨酸乙酯、乙酸苯乙酯、月桂酸乙酯、苯丙酸乙酯、乙醛、3-甲基丁醛、己醛、庚醛、辛醛、壬醛、糠醛、苯甲醛、苯乙醛、(E,E)-2,4-癸二烯醛、2-丁醇、1-丙醇、2-甲基-1-丙醇、1-丁醇、2-甲基-1-丁醇、3-甲基-1-丁醇、2-己醇、1-戊醇、1-己醇、3-辛醇、2-壬醇、1-辛醇、1-壬醇、1-癸醇、苯乙醇、乙酸、己酸、癸酸、2-庚酮、3-羟基-2-丁酮、3-乙酰基-2-丁酮、2-十一烷酮、香叶基丙酮、4-甲基愈创木酚、4-乙基愈创木酚、2-丁基呋喃、2-戊基呋喃、乙缩醛、2,5-二甲基吡嗪、四甲基吡嗪、二甲基三硫，均为色谱纯，北京百灵威科技有限公司。
1.2 仪器与设备
GC×GC-TOF/MS系统包括Agilent 7890B型气相色谱仪(美国Agilent公司)，配置第二柱温箱(适应第二维色谱柱的温度变化)、四喷口液氮型调制器及Pegasus 4D型飞行时间质谱仪(美国LECO公司)。
50/30 μm DVB/CAR/PDMS萃取头，固相微萃取手动进样器，美国Supelco公司。
1.3 实验方法
1.3.1 样品前处理
顶空固相微萃取法。分别采用50/30 μm DVB/CAR/PDMS萃取头萃取2种原酒中的挥发性成分。吸取老五甑工艺原酒样品2.27 mL放入40 mL的顶空样品瓶中，加入超纯水12.73 mL稀释至酒精度10% vol。吸取三排净工艺原酒样品2.21 mL放入另一40 mL的顶空样品瓶中，加入煮沸的超纯水12.79 mL稀释至酒精度10% vol。分别加入10 μL质量浓度为229.00 mg/L的内标物丙酸辛酯(溶剂为无水乙醇)，并加入一定量的氯化钠至饱和。分别在45 ℃的恒温水浴中平衡20 min，插入已经在250 ℃下老化10 min的萃取头，在45 ℃的恒温水浴中萃取40 min。萃取结束后，将萃取头放在GC×GC进样口热解析5 min，进行GC×GC-TOF/MS分析。每种原酒样品配制3个平行样，分别萃取进样分析。数据结果取3个平行样的平均值。
1.3.2 仪器分析条件
二维气相色谱系统。第一维柱DB-WAX(30 m×0.25 mm×0.25 μm)，第二维柱DB-5 (1.64 m×0.1 mm×0.1 μm)，均购于美国Agilent公司，两根色谱柱通过毛细管柱连接器以串联方式连接。载气He，纯度99.999%，流速1 mL/min；进样口温度250 ℃；压强30 PSI (206.85 kPa)；不分流手动进样；主柱温箱升温程序：初始温度45 ℃，以3 ℃/min升至150 ℃，保持1 min，以5 ℃/min升至230 ℃，保持10 min；第二柱温箱升温程序：高于主柱温箱5 ℃。调制器温度：高于主柱温箱15 ℃。调制周期6 s；冷吹时间700 ms，冷脉冲是干燥氮气经过液氮冷却后由调制器调制形成。
质谱分析条件。电子轰击(election ionization,EI)离子源，电子能量70 eV，传输线温度250 ℃，离子源温度250 ℃，检测器电压-1 400 V，质量扫描范围35～400 u，采集频率100 Hz。
1.4 定性分析方法
GC×GC-TOF/MS检测的总离子流图采用LECO Chroma TOF version 4D软件处理数据，并采用NIST14谱库检索，选取匹配度在800以上的化合物，剔除没有风味贡献的可疑化合物和柱流失物质。
在相同GC×GC-TOF/MS条件下进样C6～C30正构烷烃混合物，将组分保留指数(retention index, RI)与文献RI对比，取绝对值相差10以内的化合物。
在相同GC×GC-TOF/MS条件下进样83种化合物标准品，通过与未知化合物的保留时间和质谱图对比进行标准品定性，一维保留时间相同，二维保留时间相差0.5 s以内。
1.5 定量分析方法
原酒中各挥发性化合物的含量是通过在稀释后的萃取液中加入10 μL质量浓度为229.00 mg/L的内标物丙酸辛酯(溶剂为无水乙醇)进行内标法定量，按式(1)计算各挥发性成分的含量。
(1)
式(1)中，ρi为挥发性化合物在原酒中的质量浓度，μg/L；Ai为化合物的峰面积；A0为内标物的峰面积；ρ0为内标物在稀释后的萃取液中的质量浓度，μg/L；m为酒样稀释倍数。
2 结果与分析
2.1 GC×GC-TOF/MS分析结果
混蒸混烧老五甑工艺和清蒸清烧三排净工艺2种老白干香型原酒挥发性成分的GC×GC-TOF/MS总离子流图见图1，图中每个斑点代表一种化合物，通过NIST14谱库检索分别得到1 440个和1 628个色谱峰，经扣除柱流失，合并相同峰，选取匹配度大于800的化合物并采用保留指数进一步定性，最终2种生产工艺分别得到234种和253种挥发性成分(见表1)。通过与标准品的保留时间和质谱图对比，对其中的83种化合物做了进一步结构确认。
图1 2种工艺老白干原酒挥发性成分的GC×GC-TOF/MS总离子流图
Fig.1 GC×GC-TOF/MS image of total ion chromatogram of volatiles in Laobaigan base Baijiu from two kinds of processes
由图1可以看出，全二维气相色谱有效地解决了传统一维气相色谱常见的化合物共流出现象，使一维共流出化合物在第二维色谱柱上得到了分离。如表1所示，乙酸乙酯和乙缩醛的一维时间均为406 s，应用二维气相色谱成功将其分离，这2种化合物分别呈菠萝味和水果香，对老白干的水果香气均具有一定的贡献；壬酸乙酯和(E)-2-壬烯醛的一维时间均为1 827 s，分别呈水果香玫瑰香和黄瓜味青草香；辛酸异戊酯和1-壬醇分别呈水果香和青草香，其一维时间均为2 121 s；除此之外，还有2-壬醇和苯甲醛(1 785 s)、庚醛和2-庚酮(931 s)、2-壬酮和壬醛(1 540 s)、香叶基丙酮和2-甲氧基苯酚(2 527 s)等，均在二维上得到了很好的分离。
2.2 2种工艺老白干原酒挥发性成分分析结果
这2种原酒同属于老白干香型，因此具有绝大多数的共有组分，但是由2种不同的酿造工艺酿制而成，因此挥发性成分在数量及含量上的不同，对整体风味的贡献有所差异。如表1，采用强极性柱(DB-Wax)为第一维色谱柱，弱极性柱(DB-5)为第二维色谱柱进行GC×GC-TOF/MS分析，在老五甑工艺原酒中鉴定出234种挥发性成分，包括85种酯类、33种醛类、38种醇类、9种酸类、30种酮类、4种酚类、5种醚类、8种呋喃类、9种缩醛类、8种含氮类、10种含硫类、2种内酯类和3种萜烯类挥发性风味化合物。在三排净工艺原酒中鉴定出253种挥发性成分，包括83种酯类、34种醛类、42种醇类、11种酸类、27种酮类、5种酚类、7种醚类、8种呋喃类、11种缩醛类、8种含氮类、6种含硫类、3种内酯类和8种萜烯类挥发性风味化合物。2种工艺老白干原酒中共鉴定出273种化合物，有214种化合物为2种工艺老白干原酒共有，这些共有的化合物主要为酯类、醛类、醇类以及酮类化合物，它们赋予了老白干香型白酒香气清雅，酒体醇厚细腻的整体风格[21]。
2种工艺老白干原酒中酯类化合物检测到的数量最多(85种)且含量最高，这一结果与其他香型白酒结论相一致[10,15,22]。2种工艺老白干原酒中含量均较高(≥55.23 mg/L)的为乳酸乙酯，其次是乙酸乙酯、癸酸乙酯、辛酸乙酯、乙酸异戊酯。酯类化合物使老白干香型白酒呈现出以乳酸乙酯和乙酸乙酯为主体的酯香气[21]。比较2种工艺老白干原酒，酯类化合物的总含量(图2)在三排净工艺原酒中(2.08 g/L)约为老五甑工艺原酒(1.60 g/L)的1.30倍。如图1所示黑色曲线区域内的大多数酯类化合物，在三排净工艺原酒中含量大于老五甑工艺原酒，赋予三排净工艺原酒更明显的甜香、花香和果香，酒体口感比较纯净清雅，可能由于三排净工艺发酵周期比老五甑工艺长，而酯类化合物主要是通过酵母和其他微生物发酵形成[23-24]。辛酸甲酯(橘子香)、异戊酸乙酯和己酸丙酯(水果香)在三排净工艺原酒中含量高于老五甑工艺原酒达10倍以上；乙酸癸酯(橘子香)和棕榈酸乙酯(奶油香)只在三排净工艺原酒中检测到且含量较高(≥4.69 mg/L)。
在2种工艺老白干原酒中还检测到较多的醛类化合物(35种)、醇类化合物(44种)以及酮类化合物(35种)。白酒中的醛类化合物主要呈现青草香、麦芽香[25]。醛类化合物中含量较高的(≥22.36 mg/L)为糠醛(杏仁香)、苯乙醛(玫瑰香)和乙醛(青草香)。其中，乙醛被认为是协调老白干香型白酒风味的重要化合物[19]。由图2可见，对比2种工艺原酒，在醛类化合物的总含量上，老五甑工艺原酒(0.26 g/L)约为三排净工艺原酒(0.16 g/L)的1.64倍，使得老五甑工艺原酒的青香、麦芽香、坚果香更为突出，可能由于三排净工艺采用热水润料、清蒸原辅料，损失了部分醛类化合物的前体物质。其中，3-糠醛(杏仁香)、(E,E)-2,4-庚二烯醛(坚果香)、(E)-2-壬烯醛(青草香)以及藏红花醛(甜香)在老五甑工艺原酒中含量均高出三排净工艺原酒7倍以上，赋予老五甑工艺原酒更丰富的香气。
含量较高的醇类化合物(≥15.75 mg/L)为3-甲基-1-丁醇、2-甲基-1-丁醇和2-甲基-1-丙醇，主要呈现水果香、麦芽香、醇香。在三排净工艺原酒中醇类总量(227.62 mg/L)约为老五甑工艺原酒(178.57 mg/L)的1.27倍，使得三排净工艺原酒中水果香、醇香更为突出。对于酮类化合物，含量较高的(≥12.93 mg/L)为2-十一烷酮(水果香)、3-乙酰基-2-丁酮(甜香)以及香叶基丙酮(青草香)。在三排净工艺原酒中酮类化合物的含量(103.86 mg/L)略高于老五甑工艺原酒(94.55 mg/L)。其中，2-丁醇(醇香)、6-甲基-2-庚酮(樟脑香)、3-羟基-2-丁酮(奶油香)和2,2,6-三甲基环己酮(蜂蜜香)在三排净工艺原酒中的含量均高出老五甑工艺原酒的6倍以上。另外，β-大马酮(≥6.25 mg/L)呈苹果香、玫瑰香、蜂蜜味，具有极低的阈值(0.1 μg/L)，对白酒风味具有较大的贡献[26-27]。
酸类、酚类、醚类、呋喃类、缩醛类、含氮类、含硫类、内酯类和萜烯类化合物检测到的数量均较少(≤11种)；除缩醛类化合物(总量≥115.55 mg/L)外，其余上述各类化合物总量均较低。在缩醛类化合物中，乙缩醛含量较高(≥57.34 mg/L)，能够增强酒体放香，使老白干酒体口感更醇厚丰满，是白酒老熟的重要标志之一[21]。对比2种工艺老白干原酒，老五甑工艺原酒中含硫类化合物在数量上高于三排净工艺原酒，三排净工艺原酒中萜烯类化合物在数量上高于老五甑工艺原酒，其他类化合物数量差别不大。在各类化合物总量上(图2)，老五甑工艺原酒的酚类、含氮类和含硫类化合物分别为三排净工艺原酒的2.34倍、1.43倍和1.73倍，赋予酒体烟熏香、坚果香、烤香、硫味等香气，使老五甑工艺原酒香气更为丰富，酒体口感醇厚丰满，可能由于老五甑工艺采用混蒸混烧、续茬发酵，将原辅料中的复杂香气蒸入酒中。而在三排净工艺原酒中呋喃类、内酯类和萜烯类化合物分别为老五甑工艺原酒的1.31倍、1.65倍和1.57倍，使得三排净工艺原酒中甜香、水果香更为突出。其中，4-甲基愈创木酚(烟熏香)、2,5-二甲基吡嗪(坚果香、烤香)、3-甲硫基丙醛(煮土豆)以及3-甲硫基丙酸乙酯(蒜香)[28]，这些香气化合物在老五甑工艺原酒中含量更为较高；而2-丁基呋喃(水果香、甜香)、γ-癸内酯(水果香)[29]、α-蒎烯(松木香)[15]，在三排净工艺原酒中含量更高。
表1 2种工艺老白干原酒挥发性成分分析结果
Tab.1 Results of volatile compounds in Laobaigan base Baijiu of two kinds of processes
序号化合物名称t保留/s(一维时间,二维时间)匹配度鉴定方式文献RI/计算RIρ/(μg·L-1)老五甑工艺三排净工艺酯类(85种)1甲酸乙酯343,1.620936MS,RI,S814/8185785.04±409.064891.64±345.892乙酸甲酯350,1.620955MS,RI825/827144.65±13.62793.28±56.093乙酸乙酯406,1.850967MS,RI,S900/893441826.57±24383.85462816.49±29058.434丙酸乙酯490,2.130974MS,RI951/9609271.75±655.619419.94±666.095异丁酸乙酯504,2.400954MS,RI,S971/9701843.94±130.399669.01±683.706乙酸丙酯511,2.110938MS,RI977/97511323.53±800.6911888.52±840.657乙酸仲丁酯532,2.330906MS,RI1000/990572.74±43.691198.73±84.768丙烯酸乙酯539,2.000909MS,RI,S1005/995694.36±49.10262.62±18.579乙酸异丁酯567,2.390936MS,RI,S1022/101217963.02±1270.1831767.19±2246.2810丁酸乙酯616,2.540947MS,RI,S1035/103916794.72±1187.5733144.53±2343.6711丙酸丙酯630,2.520962MS,RI,S1045/1048114.10±8.07781.43±55.26122-甲基丁酸乙酯644,2.890967MS,RI,S1048/10551030.77±72.894506.25±318.6413甲酸异戊酯672,2.320905MS,RI,S1070/1069110.54±7.82209.97±14.8514异戊酸乙酯672,2.840884MS,RI,S1064/1069457.28±32.335127.55±362.5715乙酸丁酯679,2.460945MS,RI1075/10762133.88±150.895466.08±386.5116异丁酸异丁酯714,3.400937MS,RI,S1092/1096181.34±17.51428.57±30.3017乙酸仲戊酯770,2.700901MS,RI1126/1116269.48±19.06-18丁酸丙酯783,3.090912MS,RI,S1130/1120300.26±26.37626.53±44.3019乙酸异戊酯784,2.940949MS,RI,S1121/112155225.43±3622.19118712.63±8394.2520乙酸叔戊酯787,2.860941MS,RI1126/1123949.58±87.844768.38±337.1821戊酸乙酯812,3.000950MS,RI,S1134/11336144.43±434.4819976.14±1412.5322丙酸丁酯826,2.960927MS,RI,S1138/113549.20±3.48266.81±18.8723乙酸戊酯840,2.640900MS,RI1140/1140772.01±54.592789.96±197.2824丁酸异丁酯868,3.390914MS,RI1146/1149131.35±8.861228.60±86.88252-甲基丁酸异丁酯910,3.920883MS,RI1169/1163-288.25±20.3826己酸甲酯938,2.830910MS,RI,S1176/1172-290.04±20.5127异丁酸异戊酯952,3.870920MS,RI1183/1183568.77±47.892275.09±160.8728丁酸丁酯1015,3.360919MS,RI1220/1218159.35±11.27943.9±66.7429丁酸异戊酯1070,3.820931MS,RI1266/1266322.51±22.80-30己酸乙酯1071,3.210963MS,RI,S1232/123419667.50±1592.7826476.57±2407.7131丁酸戊酯1134,3.720918MS,RI1287/1277836.25±76.466690.92±473.1232乙酸己酯1155,3.100945MS,RI,S1285/12912128.71±150.5211619.47±821.62332-甲基丁酸异戊酯1160,4.240908MS,RI1285/1295167.79±12.78470.17±33.2534异戊酸异戊酯1211,4.090922MS,RI1312/1311-189.19±13.3835(Z)-3-己烯酸乙酯1225,2.840935MS,RI1305/1315809.12±57.215427.52±383.7836己酸丙酯1274,3.640947MS,RI,S1326/132768.09±4.812717.58±192.1637乳酸乙酯1330,1.830946MS,RI,S1341/1342400757.00±31356.53480654.17±25876.2038丙酸己酯1330,3.540832MS,RI1344/1342-105.21±7.4439庚酸乙酯1337,3.510952MS,RI,S1342/13445005.90±353.9747350.66±3348.2040己酸异丁酯1365,4.050933MS,RI,S1347/1351669.19±4.895761.31±407.3941戊酸异戊酯1386,3.960913MS,RI1346/1356272.27±5.111803.76±127.5542辛酸甲酯1456,3.320943MS,RI,S1374/137499.66±7.052183.33±154.3843己酸丁酯1526,3.820826MS,RI1392/139368.79±4.86626.14±44.27
续表1
序号化合物名称t保留/s(一维时间,二维时间)匹配度鉴定方式文献RI/计算RIρ/(μg·L-1)老五甑工艺三排净工艺44辛酸乙酯1603,4.680956MS,RI,S1433/143187018.06±6153.11108417.97±7666.3145己酸异戊酯1645,4.150941MS,RI,S1460/14582663.11±117.624405.79±1867.1746乙酸辛酯1680,3.450909MS,RI,S1471/1481694.90±49.146577.48±465.1047辛酸丙酯1784,4.020937MS,RI1526/1520343.33±24.282667.34±188.6148乙酸糠酯1813,1.930939MS,RI1534/15362882.24±203.81289.92±20.5049壬酸乙酯1827,4.150940MS,RI,S1541/154147161.12±3334.7988239.77±6239.49502-羟基-4-甲基戊酸乙酯1841,2.220902MS,RI1545/154547515.77±3359.8719332.52±1367.0251辛酸异丁酯1862,4.410914MS,RI,S1550/15531316.70±93.116742.55±476.7752乳酸异戊酯1904,2.170902MS,RI1570/156827948.46±1976.2523852.18±1686.653丙二酸二乙酯1911,2.050890MS,RI1572/1570281.33±19.89147.86±10.4654乙酸壬酯1925,3.610905MS,RI,S1575/15752416.22±170.8516212.92±1146.4355癸酸甲酯1967,3.600911MS,RI,S1597/1590500.72±35.412688.26±190.0956己酸己酯2002,4.180914MS,RI,S1612/1607518.55±36.67542.83±38.3857糠酸乙酯2016,1.950803MS,RI1611/16106052.36±399.681220.34±86.2958苯甲酸甲酯2023,2.120882MS,RI1623/1613297.84±21.06204.91±14.4959癸酸乙酯2086,4.630947MS,RI,S1648/1643166759.91±8254.19110344.8±5461.7960辛酸异戊酯2121,4.480927MS,RI1651/16598018.12±658.895535.78±320.7361苯甲酸乙酯2135,2.340951MS,RI,S1672/166654943.85±3885.1260614.94±4286.1262琥珀酸二乙酯2149,2.280971MS,RI,S1667/167325199.22±1781.8526733.15±1890.3263乙酸癸酯2163,3.770875MS,RI1683/1679-4686.27±331.37649-癸烯酸乙酯2184,3.570864MS,RI1685/16892116.90±149.692089.25±147.7365(E)-4-癸烯酸乙酯2191,3.600880MS,RI1682/16926205.95±438.832385.61±202.5566癸酸丙酯2261,4.210944MS,RI,S1725/1723528.85±37.401604.26±113.4467乙酸苯甲酯2268,2.060917MS,RI1733/1726623.41±44.08104.10±7.3668十一酸乙酯2303,3.940914MS,RI,S1737/17425373.19±379.9411472.69±811.2469癸酸异丁酯2331,4.310909MS,RI,S1750/1754598.81±42.341405.63±99.3970水杨酸甲酯2380,2.030936MS,RI1778/1775238.85±16.89248.48±17.5771甲酸-2-苯乙酯2394,1.950899MS,RI1784/1781458.91±23.9688.64±6.2772苯乙酸乙酯2394,2.140928MS,RI,S1785/17815553.52±392.699048.74±639.8473月桂酸甲酯2429,3.390915MS,RI1793/1796-257.76±18.2374水杨酸乙酯2450,2.150889MS,RI,S1817/1807285.02±20.15199.87±14.1375乙酸苯乙酯2457,2.080907MS,RI,S1820/181256661.45±4006.5751796.15±3662.5476月桂酸乙酯2534,3.380907MS,RI,S1856/185817954.78±1269.59114085.82±8067.0977癸酸异戊酯2555,3.710907MS,RI1863/1871790.46±55.893462.96±244.8778乙酸月桂酯2590,3.180831MS,RI1895/1892-159.97±11.3179苯丙酸乙酯2593,2.140919MS,RI,S1886/18946683.31±472.588739.36±617.9780苯甲酸异戊酯2632,2.310924MS,RI1928/19212230.44±157.721600.81±113.1981丁酸苯乙酯2709,2.160881MS,RI1978/1987139.36±12.89672.28±47.5482(E)-肉桂酸乙酯2891,1.940884MS,RI2095/2093-794.52±56.1883(Z)-肉桂酸乙酯2947,1.890906MS,RI2123/2124-196.78±13.9184己酸苯乙酯3003,2.190886MS,RI2160/215584.30±5.96343.38±24.2885棕榈酸乙酯3094,3.250911MS,RI2220/2210-34038.61±2406.89小计1594754.192080867.38醛类(35种)86乙醛287,1.500977MS,RI,S744/74445004.33±3500.5222359.17±1739.14
续表1
序号化合物名称t保留/s(一维时间,二维时间)匹配度鉴定方式文献RI/计算RIρ/(μg·L-1)老五甑工艺三排净工艺87丙醛310,1.580932MS,RI762/762217.11±16.89106.34±9.64882-甲基丙醛336,1.700955MS,RI812/8105935.35±461.664194.31±326.24892-甲基丙烯醛375,1.690945MS,RI871/861439.16±34.16207.78±16.26902-甲基丁醛427,1.990918MS,RI908/9157963.04±619.384125.75±320.91913-甲基丁醛434,1.950946MS,RI,S916/92223212.46±1805.5116205.99±1260.5392戊醛518,2.020890MS,RI984/9801422.01±110.611144.96±89.0693(E)-2-丁烯醛623,1.790931MS,RI1046/10444253.91±330.881364.76±106.1594己醛700,2.350939MS,RI,S1080/10884616.90±359.111582.71±123.1195庚醛931,2.680805MS,RI,S1180/11701686.50±131.18912.76±71.0096(Z)-4-庚烯醛1078,2.370815MS,RI1244/1239147.33±11.4662.61±4.8797辛醛1197,2.920946MS,RI,S1301/1307911.01±70.86523.93±40.7598(Z)-2-庚烯醛1245,2.420903MS,RI1319/13202130.19±165.69687.33±45.6899壬醛1540,2.900959MS,RI,S1390/139613367.90±1039.7814414.52±1121.19100(E)-2-辛烯醛1561,2.560934MS,RI1414/14043847.19±299.242062.98±160.461013-糠醛1607,1.690890MS,RI1426/1434782.79±60.89107.93±8.40102糠醛1631,1.740952MS,RI,S1439/144945242.25±3519.0239949.35±3107.33103(E,E)-2,4-庚二烯醛1722,2.100896MS,RI1505/15022371.60±184.47182.00±14.16104癸醛1736,3.270921MS,RI1500/15092530.46±196.823115.45±242.33105苯甲醛1785,1.930961MS,RI,S1526/152621683.67±1686.596196.88±443.11106(E)-2-壬烯醛1827,2.720940MS,RI1532/15418648.59±672.70753.08±58.581075-甲基糠醛1904,1.820959MS,RI1567/15681184.89±92.16633.79±49.30108(E,Z)-2,6-壬二烯醛1946,2.430922MS,RI1587/15831164.88±90.61359.43±27.96109十一醛1988,3.400938MS,RI1598/1597892.78±69.44493.35±38.37110β-环柠檬醛2037,2.730903MS,RI1629/1619588.20±45.75650.10±50.57111(E,E)-2,4-辛二烯醛2053,2.220868MS,RI1619/1627276.01±21.4796.44±7.50112(Z)-2-癸烯醛2079,2.810913MS,RI1644/16372032.62±158.101073.35±83.491134-甲基苯甲醛2080,2.040943MS,RI1643/16401282.24±84.18830.21±64.57114藏红花醛2085,2.510943MS,RI1648/16422074.54±161.36150.84±3.95115苯乙醛2162,1.930953MS,RI,S1680/167845249.52±3519.5928511.12±2217.64116(E,E)-2,4-壬二烯醛2212,2.380891MS,RI1710/17021920.55±149.38684.39±53.23117十二醛2233,3.560914MS,RI1718/1710-279.10±21.711182-十一烯醛2275,2.680923MS,RI1745/1735924.34±71.90-119(E,E)-2,4-癸二烯醛2450,2.260930MS,RI,S1805/18076651.33±517.353926.86±305.44120(E)-肉桂醛2760,2.240911MS,RI2015/2011-1469.42±114.29小计260655.65159418.99醇类(44种)1212-丙醇547,1.920853MS,RI992/9991898.40±161.082363.84±200.581222-丁醇595,1.730960MS,RI,S1019/10281493.61±126.7411366.08±964.441231-丙醇628,1.680949MS,RI,S1037/104511482.65±974.348990.07±762.831243-戊醇770,1.860901MS,RI1108/1116-184.68±15.671252-甲基-1-丙醇777,1.690942MS,RI,S1116/111819429.68±2072.9316912.33±1435.061262-丙烯-1-醇783,1.580914MS,RI1130/1120-288.19±24.451271-丁醇854,1.750944MS,RI,S1150/11442962.17±166.503811.17±323.391281-戊烯-3-醇882,1.760907MS,RI1158/1154320.52±27.2047.71±4.051292-甲基-1-丁醇987,1.840928MS,RI,S1199/118915752.42±1244.1929521.46±2504.98
续表1
序号化合物名称t保留/s(一维时间,二维时间)匹配度鉴定方式文献RI/计算RIρ/(μg·L-1)老五甑工艺三排净工艺1303-甲基-1-丁醇1008,2.040946MS,RI,S1217/121546072.59±3909.3991574.02±7770.311312-己醇1020,1.960931MS,RI,S1226/1235160.73±13.64-1323-甲基-3-丁烯-1-醇1090,1.750914MS,RI1240/1250351.48±29.82173.68±15.391331-戊醇1106,1.840929MS,RI,S1252/12581991.76±168.921637.60±138.95134环戊醇1239,1.810913MS,RI1323/1318125.65±10.66119.06±10.10135(Z)-2-戊烯-1-醇1274,1.740881MS,RI1329/1327177.07±15.0237.84±3.211363-甲基-2-丁烯-1-醇1281,1.750892MS,RI1324/1329324.26±27.51146.61±12.441373-甲基-1-戊醇1295,1.930940MS,RI1331/1333212.22±18.01560.70±47.581384-甲基-1-戊醇1307,1.920934MS,RI1330/1335263.59±22.37270.98±22.991391-己醇1365,1.980943MS,RI,S1353/135113513.45±1146.6511540.98±979.281403-己烯-1-醇1410,1.850941MS,RI1374/1364370.27±48.39-1413-乙氧基-1-丙醇1428,1.810899MS,RI1364/1367235.47±19.98238.50±20.24142(Z)-3-己烯醇1442,1.860939MS,RI1373/1371-202.14±17.151433-辛醇1470,2.350940MS,RI,S1385/1378632.70±53.69338.48±28.72144(Z)-芳樟醇1610,2.610837MS,RI1433/143531.49±2.67133.61±11.341451-辛烯-3-醇1610,4.830888MS,RI1442/143512552.54±1065.125102.77±432.981461-庚醇1624,2.050959MS,RI1447/14452560.98±217.311649.14±139.931474-庚醇1729,2.050819MS,RI1497/1507154.09±13.0768.26±5.791482-壬醇1785,2.400953MS,RI,S1524/15263023.17±256.52216.49±18.37149芳樟醇1841,2.390881MS,RI1540/1545797.77±67.69473.68±40.191501-辛醇1876,2.180949MS,RI,S1560/15589196.61±780.366841.81±580.551512,3-丁二醇1911,1.550948MS,RI1570/15702789.86±236.73840.94±71.36152松油烯-4-醇1988,2.580868MS,RI1591/1597196.03±16.63107.18±9.09153乙二醇2023,1.460922MS,RI1621/1613-180.45±15.31154(E)-2-辛烯醇2029,2.020922MS,RI1620/16161912.80±162.31710.76±60.311552-呋喃甲醇2107,1.570941MS,RI1655/1653617.88±52.43196.37±16.661561-壬醇2121,2.280964MS,RI,S1656/165911609.84±985.139567.51±811.83157(Z)-3-壬烯醇2170,2.170941MS,RI1682/16821009.68±85.671115.95±94.691582,6-二甲基-4-庚醇2324,2.490834MS,RI1741/1751-460.46±89.981591-癸醇2345,2.300935MS,RI,S1752/17603309.49±280.823184.38±270.2160橙花醇2422,2.030900MS,RI1786/1793150.36±12.76265.80±22.55161香叶醇2533,1.950910MS,RI1860/1857907.18±76.981753.4±148.78162苯乙醇2625,1.660957MS,RI,S1915/19169712.24±824.1114015.84±1265.651631,4-丁二醇2632,1.470916MS,RI1923/1921-191.16±16.22164丙三醇3150,1.410920MS,RI2301/2303269.92±22.9220.56±18.71小计178572.62227622.64酸类(11种)165乙酸1617,1.460953MS,RI,S1446/144022174.58±2038.3715503.82±1425.171662-甲基丙酸1918,1.530886MS,RI1581/1573646.27±59.41440.22±40.47167丁酸2065,1.520866MS,RI1637/1634969.15±89.09447.04±41.091682-甲基丁酸2147,1.560885MS,RI1662/1672-436.74±40.151693-甲基丁酸2156,1.550808MS,RI1680/16761214.88±111.681399.74±128.67170戊酸2324,1.540913MS,RI1744/1751397.39±36.53395.23±29.90171己酸2520,1.550935MS,RI,S1854/18502235.03±113.536514.02±598.79172庚酸2716,1.530917MS,RI1981/1991237.35±17.75314.07±28.87
续表1
序号化合物名称t保留/s(一维时间,二维时间)匹配度鉴定方式文献RI/计算RIρ/(μg·L-1)老五甑工艺三排净工艺173辛酸2856,1.580922MS,RI2067/20711358.99±124.92943.41±86.72174壬酸3010,1.570885MS,RI2158/2159-668.70±61.47175癸酸3143,1.600908MS,RI,S2270/2264993.46±54.552803.21±257.68小计30227.1029866.20酮类(35种)176丙酮336,1.580964MS,RI814/810645.23±63.87590.63±58.471772,3-丁二酮495,1.680925MS,RI962/955401.82±39.78199.73±16.291782-戊酮518,1.980928MS,RI970/98092.40±9.15235.52±23.321793-甲基-3-丁烯-2-酮525,1.890901MS,RI987/985110.05±10.89-1804-甲基-2-戊酮560,2.190891MS,RI1002/1008-118.80±11.761811-戊烯-3-酮565,1.910912MS,RI1018/1010471.57±46.68-1822,3-戊二酮620,1.890921MS,RI1050/1043587.95±58.20-1832-甲基-1-戊烯-3-酮645,2.190914MS,RI1068/1058224.19±22.19-184(E)-3-戊烯-2-酮805,1.940955MS,RI1121/1131753.77±54.822377.07±255.12185环戊酮925,2.030937MS,RI1176/1168782.42±77.46496.7±49.171862-庚酮931,2.590905MS,RI,S1180/11705800.91±475.274900.18±485.091876-甲基-2-庚酮1071,2.810911MS,RI1236/123495.59±9.46636.91±63.051883-辛酮1113,3.010889MS,RI1261/1263508.26±50.321559.91±154.421895-甲基-2-庚酮1113,2.820876MS,RI1256/1263-103.04±10.201902-辛酮1190,2.830931MS,RI1314/13063754.78±371.74701.82±465.461913-羟基-2-丁酮1197,1.660900MS,RI,S1312/1307122.90±12.17890.53±88.161922,3-辛二酮1225,2.570902MS,RI1315/13151243.90±123.14-1931-辛烯-3-酮1232,2.630907MS,RI1317/13171364.45±135.071275.01±126.221942,2,6-三甲基环己酮1281,3.070940MS,RI1333/132985.45±8.46558.83±55.321956-甲基-5-庚烯-2-酮1323,2.510858MS,RI1341/13403194.52±316.242836.30±280.781965-甲基-2-己酮1456,3.030899MS,RI1364/1374-715.06±70.791973-乙酰基-2-丁酮1503,2.150864MS,RI,S1389/138728195.37±2791.212927.79±1279.791982-壬酮1540,3.180862MS,RI1386/1396487.11±44.261449.80±143.521992-环己烯酮1615,2.250921MS,RI1424/1434163.72±16.21-2002-烯丙基-4-酮1654,2.710952MS,RI1466/14641256.52±124.391215.37±120.322013-壬烯-2-酮1720,2.660902MS,RI1506/1501756.48±74.89-2026-十一烷酮1806,3.680916MS,RI1527/153488.49±8.76184.71±18.29203(E,E)-3,5-辛二烯-2-酮1860,2.230904MS,RI1562/1552675.83±66.90-2046-甲基-3,5-庚二烯-2-酮1960,2.190910MS,RI1582/15872273.19±225.03703.18±69.61205异佛尔酮1974,2.310916MS,RI1595/1592631.37±62.50486.54±48.172062-十一烷酮1974,3.340928MS,RI,S1599/159217350.99±1717.6638693.64±3830.48207苯乙酮2093,1.980939MS,RI1645/1646-784.36±77.65208对甲基苯乙酮2331,2.030885MS,RI1761/1754-123.17±11.18209β-大马酮2471,2.530911MS,RI1814/18207585.33±750.916249.95±618.71210香叶基丙酮2527,2.610947MS,RI,S1852/185414841.69±1469.2518848.43±1865.9小计94546.25103862.98酚类(5种)2112-甲氧基苯酚2527,1.670938MS,RI1862/185473.89±7.84175.07±18.572124-甲基愈创木酚2688,1.690927MS,RI,S1959/19611788.77±189.73138.33±14.672134-乙基愈创木酚2800,1.740967MS,RI,S2033/20365220.60±553.732060.29±218.53
续表1
序号化合物名称t保留/s(一维时间,二维时间)匹配度鉴定方式文献RI/计算RIρ/(μg·L-1)老五甑工艺三排净工艺2144-甲基苯酚2870,1.500931MS,RI2076/2080177.05±12.4273.88±7.842154-乙基苯酚3058,2.670849MS,RI2190/2185-656.49±48.42小计7260.313104.06醚类(8种)216乙醚266,1.610922MS,RI633/633510.34±32.48743.45±72.77217乙烯基乙醚280,1.610977MS,RI656/656-347.28±98.47218四氢呋喃385,1.870952MS,RI870/873-240.43±13.60219二乙二醇乙醚2023,1.820914MS,RI1619/1613-180.69±15.332204-乙烯基苯甲醚2156,2.190922MS,RI1686/16761598.41±62.91765.18±247.89221邻苯二甲醚2254,2.010924MS,RI1717/1720469.25±29.86349.03±22.21222间苯二酚二甲醚2310,2.020894MS,RI1735/1745147.98±9.4229.28±1.86223二乙二醇丁醚2355,1.890934MS,RI1779/1769486.83±38.85-小计3212.813655.34呋喃类(9种)224呋喃322,1.590889MS,RI797/802130.35±10.78419.03±35.022252-甲基呋喃378,1.790949MS,RI866/864471.45±26.67867.13±49.052262-乙基呋喃455,2.190932MS,RI955/955225.49±11.16-2272-丙基呋喃602,2.460950MS,RI1027/1032-207.71±11.752282-乙烯基呋喃679,1.980902MS,RI1075/1076642.01±36.32471.79±26.692292-丁基呋喃798,2.920956MS,RI,S1123/1129220.05±12.451319.38±74.642302-戊基呋喃1043,3.310930MS,RI,S1238/12288074.07±456.7410736.89±607.372312-乙酰基呋喃1743,1.800921MS,RI1510/15121159.18±65.57605.02±34.232322-丙酰基呋喃1911,1.930925MS,RI1563/1570244.11±24.1738.08±3.77小计11166.7114665.03缩醛类(11种)233乙醛乙基甲基缩醛364,2.010916MS,RI865/8551983.65±98.192084.39±103.17234乙缩醛406,2.400953MS,RI,S894/89365212±3227.8357339.73±2838.17235丙醛二乙基乙缩醛490,2.890928MS,RI950/960416.49±20.62275.42±13.63236丁醛二乙缩醛518,3.400841MS,RI979/980-3855.10±240.32237异丁醛二乙缩醛518,3.600850MS,RI970/980-4513.55±223.41238异戊醛二乙缩醛686,4.280877MS,RI1074/108021985.58±1088.2318079.55±894.89239乙醛乙基戊基缩醛742,4.250902MS,RI1104/11044507.30±223.105183.84±256.59240己醛二乙缩醛1064,4.930835MS,RI1241/12314547.52±225.094933.29±244.192413-乙氧基丙醛二乙缩醛1239,3.520906MS,RI1308/1318227.19±11.25559.02±27.67242壬醛二乙缩醛1706,5.370884MS,RI1498/14974808.80±238.024896.14±242.35243苯乙醛二乙缩醛2254,2.880898MS,RI1717/172011862.58±587.1727260.97±1349.35小计115551.11119981.00含氮类(8种)2442-甲基吡嗪1148,1.970961MS,RI1283/1286143.02±10.1158.17±4.112452,5-二甲基吡嗪1295,2.170906MS,RI,S1333/1333289.02±20.4450.51±3.572462,6-二甲基吡嗪1309,2.150936MS,RI1339/1336388.79±30.32203.91±14.422472,3-二甲基吡嗪1358,2.140937MS,RI1346/1349195.42±6.75148.79±10.522482-乙基-6-甲基吡嗪1456,2.380914MS,RI1382/1374374.81±26.5099.58±7.04249三甲基吡嗪1505,2.340937MS,RI1395/13871558.89±96.091461.01±103.312502,3-二甲基-5-乙基吡嗪1659,2.560875MS,RI1460/1467240.26±16.99152.43±10.78
续表1
序号化合物名称t保留/s(一维时间,二维时间)匹配度鉴定方式文献RI/计算RIρ/(μg·L-1)老五甑工艺三排净工艺251四甲基吡嗪1687,2.520932MS,RI,S1478/14857153.13±152.255056.69±357.56小计10343.347231.09含硫类(11种)252甲硫醇280,1.510979MS,RI686/6961352.50±105.21668.83±129.80253二甲基硫醚295,1.620941MS,RI716/716108.03±6.11-254二甲基二硫679,2.090955MS,RI1071/1076253.26±19.70208.86±16.252552-甲基噻吩714,2.180936MS,RI1095/109643.27±3.37126.02±9.80256噻唑1075,1.750924MS,RI1244/1239368.98±30.26174.23±15.37257二甲基三硫1435,2.350927MS,RI,S1370/13691298.76±101.023467.13±269.68258甲硫基乙酸乙酯1550,2.130915MS,RI1418/1408494.04±50.41-2593-甲硫基丙醛1575,1.860909MS,RI1433/1423812.67±68.96-2602-戊基噻吩1638,3.230903MS,RI1452/1452-448.92±42.70261糠基甲基硫醚1645,2.140913MS,RI1468/1458116.76±9.91-2623-甲硫基丙酸乙酯1850,2.250926MS,RI1558/15485723.13±485.62-小计10571.406093.99内酯类(3种)263γ-丁内酯2037,1.670945MS,RI1617/161950.46±4.28104.87±8.90264γ-壬内酯2814,1.850926MS,RI2037/20451223.54±103.821949.53±165.42265γ-癸内酯2975,1.870836MS,RI2144/2140-46.20±3.92小计1274.002100.60萜烯类(8种)266α-蒎烯595,4.400909MS,RI1026/1028-105.59±9.71267α-水芹烯985,4.070852MS,RI1179/1188-236.17±21.71268β-石竹烯1932,5.250875MS,RI1587/15972510.77±230.802730.36±197.84269别香橙烯2102,4.960828MS,RI1646/1650-106.32±9.77270(E)-β-法尼烯2134,4.530852MS,RI1661/1665-111.20±10.22271γ-榄香烯2143,5.880844MS,RI1665/1670-320.45±29.46272α-石竹烯2170,4.680905MS,RI1681/1682656.20±60.321064.59±97.86273α-甜旗烯2646,2.820888MS,RI1937/1931117.23±10.78468.16±43.03小计3284.205142.84
MS为检索NIST 14质谱库鉴定；RI为核对保留指数鉴定，文献保留指数均来自NIST 14谱库；S为标准品鉴定；“-”为未检测到该化合物。
图2 老白干老五甑和三排净工艺原酒中各类挥发性成分的总量
Fig.2 Total contents of various types of volatiles in Laobaigan base Baijiu fermented by Laowuzeng and Sanpaijing processes
3 结 论
应用顶空固相微萃取结合全二维气相色谱- 飞行时间质谱从老白干混蒸混烧老五甑工艺与清蒸清烧三排净工艺2种原酒中共鉴定出273种化合物，数量及含量均较高的为酯类、醛类、醇类和酮类化合物。对比2种工艺原酒，老五甑工艺原酒中醛类、酚类、含氮类以及含硫类化合物的含量较高，使得老五甑工艺原酒酒体更具青草香、麦芽香、烟熏香、烤香以及硫香，香气更加饱满；而在三排净工艺原酒中酯类、醇类、呋喃类、内酯类以及萜烯类化合物的含量较高，使得三排净工艺原酒更具果香、花香、甜香，酒体香气更为清雅。以上研究结果为进一步探究不同酿制工艺对老白干白酒风味的形成提供理论依据。
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