Analysis of Yunnan Black Tea Aroma Characteristics Based on HS‐SPME‐GC‐MS and OAV

doi:10.15933/j.cnki.1004-3268.2025.04.017

Abstract

Abstract: In order to investigate the aroma characteristics of Yunnan black tea from different production areas in Yunnan,12 tea samples from four production areas,namely,Simao in Puer,Changning in Baoshan,Menghai in Xishuangbanna and Fengqing in Lincang，were selected as materials.The headspace‐solid phase microextraction(HS‐SPME)combined with gas chromatography‐mass spectrometry(GC‐MS)was used to separate and identify the volatile components of Yunnan black tea from different production areas on a DB‐WAX column，and the volatile components of Yunnan black tea were analysed by using aroma activity value(OAV)combined with chemometrics to determine the volatiles composition and aroma characteristics of Yunnan black tea from different production areas.The results showed that a total of 143 volatile substances，mainly alcohols，aldehydes，esters and olefins，were identified in Yunnan black tea from different production areas，and 50 substances(OAV≥1)contributing to the flavor of Yunnan black tea were screened out with the help of OAV，among which linalool and β‐ionone had a prominent position in OAV，and were important for the composition of the flavour of Yunnan black tea from different production areas.By using orthogonal partial least squares‐discriminant analysis(OPLS‐DA),combined with variable importance projection(VIP),43 differential markers were screened(VIP≥1).Based on the results of OAV and OPLS‐DA，12 characteristic differential substances of Yunnan black tea were screened：2‐methyl butyraldehyde， benzaldehyde， heptaldehyde，Z‐hex‐3‐en‐1‐ol，methyl 2‐(methylamino)benzoate，dihydroactinidolide，D‐limonene,(E)‐3，7‐dimethylocta‐1,3,6‐triene，β‐ionone，α -lonone，dihydro‐β‐ionone，and P‐cymene.Z‐hex‐3‐en‐1‐ol contributed prominently to the clear aroma of black tea from Changning production area；dihydroactinidolide and dihydro‐β‐ionone contributed prominently to the floral and fruity aroma of Menghai production area，and heptaldehyde contributed prominently to the fruity aroma of Fengqing production area.Further analysis showed that the Yunnan black tea aroma types of the four production areas were mainly floral and fruity.Combined with the cluster analysis，Changning and Fengqing production areas had floral and sweet aroma，and the fruity aroma was stronger，absence of honey notes；and the differentiated compounds of Simao and Menghai production areas were more diverse，and the composite aroma was obvious，which involved the sweet aroma，honey aroma，grassy aroma，clear aroma and fat aroma.

Key words: Yunnan black tea, Aroma characteristics, Headspace‐solid phase microextraction, Volatile substances, Orthogonal partial least squares‐discriminant analysis

摘要： 为探究云南不同产区滇红茶香气特征，选取普洱思茅、保山昌宁、西双版纳勐海和临沧凤庆4个产区12份茶样，采用顶空固相微萃取法结合气相色谱-质谱技术（HS-SPME-GC-MS）和强极性色谱柱DB-WAX分离鉴定不同产区滇红茶的挥发性成分，使用香气活性值（Odor activity value，OAV）结合化学计量学，解析不同产区滇红茶的挥发性物质构成及香气特征。结果表明，不同产区滇红茶共鉴定出143种挥发性物质，主要为醇类、醛类、酯类和烯烃类物质。借助香气活性值筛选出50种对滇红茶风味有贡献的物质（OAV≥1），其中，芳樟醇和β-紫罗酮的OAV具有突出地位，对不同产区滇红茶的风味构成均有重要作用。使用正交偏最小二乘判别分析（OPLS-DA），结合变量重要性投影值（VIP）筛选出43种差异标志物（VIP≥1）。基于OAV和OPLS-DA结果，筛选出12种滇红茶的特征性差异物质：2-甲基丁醛、苯甲醛、庚醛、叶醇、2-（甲氨基）苯甲酸甲酯、二氢猕猴桃内酯、D-柠檬烯、（E）-β-罗勒烯、β-紫罗酮、β-紫罗兰酮、β-二氢紫罗兰酮、4-异丙基甲苯。叶醇对昌宁产区红茶的清香具有突出贡献；二氢猕猴桃内酯、β-二氢紫罗兰酮对勐海产区的花香、果香具有突出贡献，庚醛对凤庆产区的果香具有突出贡献。进一步分析表明，4个产区滇红茶香型均以花香、果香为主，带甜香，再结合聚类分析，昌宁和凤庆产区有花香、甜香，果香较为强烈；思茅和勐海产区差异性化合物种类较多，复合香明显，涉及甜香、蜜香、草香、清香、脂肪香。

关键词: 滇红茶, 香气特征, 顶空固相微萃取法, 挥发性物质, 正交偏最小二乘判别分析

CLC Number:

S571.1
O657

DING Qihuan, DENG Min, SHI Dekang, SU Jianmei, GU Chonglin, LI Sijin. Analysis of Yunnan Black Tea Aroma Characteristics Based on HS‐SPME‐GC‐MS and OAV[J]. Journal of Henan Agricultural Sciences, 2025, 54(4): 167-180.

丁其欢, 邓敏, 施德康, 苏建美, 顾冲林, 李思锦. 基于HS-SPME-GC-MS 和OAV 分析云南红茶香气特征[J]. 河南农业科学, 2025, 54(4): 167-180.

Figures/Tables 3

References

［1］杨霁虹，周汉琛，刘亚芹，等.基于HS-SPME-GC-MS和OAV分析黄山地区不同茶树品种红茶香气的差异［J］.食品科学，2022，43（16）：235‐241.
YANG J H，ZHOU H C，LIU Y Q，et al.Differences in aroma components of black tea processed from different tea cultivars in Huangshan by using headspace‐solid phase microextraction‐gas chromatography‐mass spectrometry and odor activity value［J］.Food Science，2022，43（16）：235‐241.
［2］胡善国，黄建琴，雷攀登，等.不同做形干燥方式对名优祁红香气成分的影响［J］.食品工业科技，2018，39（8）：226‐231.
HU S G，HUANG J Q，LEI P D，et al.Effect of different shaping drying condition on volatil aroma components in famous Keemum black tea［J］.Science and Technology of Food Industry，2018，39（8）：226‐231.

［3］娄鹏祥. 祁门红茶发展现状与对策［J］. 安徽林业科技，2022，48（1）：60‐61.
LOU P X.Development actualities of and targeted measures for keemun black tea［J］. Anhui Forestry Science and Technology，2022，48（1）：60‐61.

［4］徐亚文，牛淼，刘娜，等. 传统滇红工夫红茶与野生滇红工夫红茶的品质分析［J］. 食品工业科技，2023，44（6）：335‐344.
XU Y W，NIU M，LIU N，et al.Quality analysis of traditional and wild Yunnan congou black tea［J］.Science and Technology of Food Industry，2023，44（6）：335‐344.

［5］LI N，CHEN M，ZHU H T，et al. Theaflavoids A‐C，new flavan‐3‐ols with potent α‐glucosidase inhibitory activity from Yunnan black tea‘Jin‐Ya’［J］.LWT，2022，168：113918.

［6］王娟，任可乐，孙杰，等.枣芽红茶与滇红茶活性成分含量测定及降糖效果对比研究［J］. 热带农业科学，2022，42（6）：76‐80.
WANG J，REN K L，SUN J，et al.Determination of active ingredients of jujube bud black tea and Yunnan black tea and comparison on hypoglycemic effect［J］.Chinese Journal of Tropical Agriculture，2022，42（6）：76‐80.

［7］刘飞，王云，张厅，等. 红茶加工过程香气变化研究进展［J］. 茶叶科学，2018，38（1）：9‐19.
LIU F，WANG Y，ZHANG T，et al. Review on aroma change during black tea processing［J］. Journal of Tea Science，2018，38（1）：9‐19.

［8］刘晓慧，张丽霞，王日为，等.顶空固相微萃取-气相色谱-质谱联用法分析黄茶香气成分［J］. 食品科学，2010，31（16）：239‐243.
LIU X H，ZHANG L X，WANG R W，et al. Analysis of volatile components of yellow tea by HS‐SPME/GC‐MS［J］.Food Science，2010，31（16）：239‐243.

［9］王秋霜，陈栋，许勇泉，等. 中国名优红茶香气成分的比较研究［J］.中国食品学报，2013，13（1）：195‐200.
WANG Q S，CHEN D，XU Y Q，et al. Comparative study on the aroma components of famous Chinese black teas［J］. Journal of Chinese Institute of Food Science and Technology，2013，13（1）：195‐200.

［10］程超，夏兰欣，杜芬妮，等.基于9种风味物质的利川红SPME优化及PLS-DA风味识别［J］. 食品科学，2021，42（6）：215‐222.
CHENG C，XIA L X，DU F N，et al. Optimization of solid phase microextraction for GC‐MS analysis of nine flavor compounds in Lichuan Hong tea and flavor discrimination by partial least squares‐discriminant analysis［J］.Food Science，2021，42（6）：215‐222.

［11］LIU P P，ZHENG P C，GONG Z M，et al.Analysis of aroma characteristics and volatilecomponents of Juhong tea，manufactured from black tea with added citrus peel［J］. Food Science，2021，42（8）：198‐205.

［12］刘盼盼，郑鹏程，龚自明，等.工夫红茶品质分析与综合评价［J］. 食品科学，2021，42（12）：195‐205.
LIU P P，ZHENG P C，GONG Z M，et al. Quality analysis and comprehensive evaluation of Chinese congou black tea［J］. Food Science，2021，42（12）：195‐205.

［13］郑芳玲，甘诗雅，赵蕾，等. 基于GC-MS/GC-O的不同地区红茶特征香气及分子感官分析［J］. 食品科学，2023，44（24）：262‐268.
ZHENG F L，GAN S Y，ZHAO L，et al.Characteristic aroma and molecular sensory analysis of black teas from different regions by gas chromatography‐massspectrometry and gas chromatography‐olfactometry［J］.FoodScience，2023，44（24）：262‐268.

［14］ZHANG J，YANG R D，CHEN R，et al.Multielemental analysis associated with chemometric techniques for geographical origin discrimination of tea leaves（Camelia sinensis）in Guizhou Province，SW China［J］.Molecules，2018，23（11）：3013.

［15］杨学博，陈秋翰，刘寿春，等. 基于GC‐IMS和OPLS‐DA 分析酵母‐藿香复合对罗非鱼脱腥效果的影响［J/OL］. 食品与发酵工业，2023：1‐11［2023‐09‐27］.http：//kns. cnki. net/KCMS/detail/detail. aspx？filename=SPFX20230922004&dbname=CJFD&dbcode=CJFQ.
YANG X B，CHEN Q H，LIU S C，et al.Effect of yeast‐Agastache rugosus complex on deodorization of tilapia based on GC‐IMS and OPLS‐DA［J/OL］.China Industrial Economics，2023：1‐11［2023‐09‐27］.http：//kns.cnki.net/KCMS/detail/detail.aspx？filename=SPFX20230922004&dbname=CJFD&dbcode=CJFQ.

［16］LIU D，QI Y M，ZHAO N，et al.Multivariate analysis reveals effect of glutathione‐enriched inactive dry yeast on amino acids and volatile components of kiwi wine［J］.Food Chemistry，2020，329：127086.

［17］SHI J， XIE D C， QI D D， et al.Methyl jasmonate‐induced changes of flavor profiles during the processing of green，oolong，and black tea［J］.Frontiers in Plant Science，2019，10：781.

［18］刘登勇，周光宏，徐幸莲.确定食品关键风味化合物的一种新方法：“ROAV”法［J］.食品科学，2008，29（7）：370‐374.
LIU D Y，ZHOU G H，XU X L.“ROAV”method：A new method for determining key odor compounds of rugao ham［J］.Food Science，2008，29（7）：370‐374.

［19］徐梦婷，谷梦雅，陈静，等.基于代谢组学的金牡丹和金观音高香红茶风味品质解析［J］.食品科学，2024，45（19）：150‐161.
XU M T，GU M Y，CHEN J，et al.Flavor quality analysis of the high‐aroma black tea cultivars ‘Jinmudan’and‘Jinguanyin’using metabolomics［J］.Food Science，2024，45（19）：150‐161.

［20］郭英杰，郭智鑫，卞建明，等. GC-MS结合ROAV分析不同干燥方式对桂花浸膏与净油香气成分的影响［J/OL］.食品科学，2024：1‐18［2024‐03‐08］. http：//kns.cnki.net/kcms/detail/11.2206.TS.20240305.0926.002.html.
GUO Y J，GUO Z X，BIAN J M，et al.The effect of different drying methods on the aroma components of Osmanthus fragrans concrete and absolute were analyzed by combing GC‐MS with ROAV analysis［J/OL］.Food Science，2024：1‐18［2024‐03‐08］. https：//kns.cnki.net/kcms/detail/11.2206.TS.20240305.0926.002.html.

［21］石亚丽，白艳，马婉君，等.安吉白茶挥发性成分及关键呈香成分分析［J］. 食品科学，2022，43（20）：261‐268.
SHI Y L，BAI Y，MA W J，et al.Analysis of volatile components and key aroma‐active compounds of anjibaicha［J］.Food Science，2022，43（20）：261‐268.

［22］张韵，李蕙蕙，周圣弘.基于OAV对3种高香种工夫红茶的香气特征分析［J］.食品研究与开发，2020，41（21）：184‐191.
ZHANG Y，LI H H，ZHOU S H.Analysis of fragrance characteristics in three congou black teas of highly fragrant species using odor active values［J］.Food Research and Development，2020，41（21）：184‐191.

［23］田军，吕海鹏，马婉君，等.基于SBSE-GC-MS的紫芽茶挥发性成分分析［J］.中国茶叶，2021，43（6）：46‐53.
TIAN J，LÜ H P，MA W J，et al.Volatile compounds of purple teas based on SBSE‐GC‐MS［J］.China Tea，2021，43（6）：46‐53.

［24］金磊，练学燕，杨植溢，等.基于HS-SPME-GC-MS分析不同茶树品种川红工夫红茶香气差异［J］.食品工业科技，2024，45（19）：268‐277.
JIN L，LIAN X Y，YANG Z Y，et al.Differences in aroma of Chuanhong congou black tea of different tea plant varieties based on HS‐SPME‐GC‐MS analysis［J］.Science and Technology of Food Industry，2024，45 （19）：268‐277.

［25］里奥·范海默特. 化合物香味阈值汇编［M］.北京：科学出版社，2015：137‐139.
VAN HEIMERT L.Compilation of compound aroma thresholds［M］.Beijing：Science Press，2015：137‐139.

［26］唐梦婷，廖献盛，谷梦雅，等.基于HS-SPME-GC-MS 分析三种茶坯窨制桂花茶的香气成分［J］.现代食品科技，2024，40（3）：247‐258.
TANG M T，LIAO X S，GU M Y，et al.Analysis of aromatic compounds in three types of tea dhools scented with osmanthus using HS‐SPME‐GC‐MS［J］.Modern Food Science and Technology，2024，40（3）：247‐258.
［27］李云飞. 基于SPME-GC-MS的云南红茶香气成分分析［D］.天津：天津科技大学，2015.

LI Y F.Analysis of Yunnan black tea aromatic components based on SPME‐GC‐MS［D］.Tianjin：Tianjin University of Science & Technology，2015.

［28］郭丽，彭群华，赵锋，等.不同等级新九曲红梅茶的风味化学特征［J］. 食品科学，2021，42（4）：215‐220.
GUO L，PENG Q H，ZHAO F，et al.Flavor chemistry characteristics of new Jiuqu Hongmei tea of different
grade levels［J］.Food Science，2021，42（4）：215‐220.

［29］彭云，李果，刘学艳，等.不同产地红茶香气品质的SPME/GC-MS分析［J］.食品工业科技，2021，42（9）：237‐244.
PENG Y，LI G，LIU X Y，et al.SPME/GC‐MS analysis of aroma quality of black tea from different producing areas［J］.Science and Technology of Food Industry，2021，42（9）：237‐244.

［30］ZHOU Z W，WU Q Y，YAO Z L，et al.Dynamics of ADH and related genes responsible for the transformation of C6‐aldehydes to C6‐alcohols during the postharvest process of oolong tea［J］.Food Science & Nutrition，2020，8（1）：104‐113.

［31］靳巧丽，姜泽东，倪辉，等.速溶乌龙茶粉挥发性成分的分析［J］.现代食品科技，2015，31（7）：372‐379.
JIN Q L，JIANG Z D，NI H，et al.Volatile components of instant oolong tea powder［J］.Modern Food Science and Technology，2015，31（7）：372‐379.

［32］刘琴.UPLC-PDA/UHPLC-Q-TOF-MS分析六大茶类中的酚酸类物质［D］.合肥：安徽农业大学，2019.
LIU Q.Analysis of phenolic acids in six type teas by UPLC‐PDA and UHPLC‐Q‐TOF‐MS［D］.Hefei：Anhui Agricultural University，2019.

［33］宛晓春. 茶叶生物化学［M］.北京：中国农业出版社，2021：203‐209.
WAN X C.Tea biochemistry ［M］.Beijing：China Agricultural Press，2021：203‐209.