Article(id=1320880709921780721, tenantId=1146029695717560320, journalId=1260987677001138203, issueId=1320880625310085394, articleNumber=null, orderNo=null, doi=10.13386/j.issn1002-0306.2025080105, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1754841600000, receivedDateStr=2025-08-11, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1792852102021, onlineDateStr=2026-10-24, pubDate=1788192000000, pubDateStr=2026-09-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792852102021, onlineIssueDateStr=2026-10-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792852102021, creator=13701087609, updateTime=1792852102021, updator=13701087609, issue=Issue{id=1320880625310085394, tenantId=1146029695717560320, journalId=1260987677001138203, year='2026', volume='47', issue='17', pageStart='1', pageEnd='596', issueExtLink='null', onlineDate='null', pubDate='1788192000000', pubDateStr='2026-09-01', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792852081848, creator='13701087609', updateTime=1792852081848, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=386, endPage=394, ext={EN=ArticleExt(id=1320880710110524402, articleId=1320880709921780721, tenantId=1146029695717560320, journalId=1260987677001138203, language=EN, title=Geographical Traceability of Yunnan Sun-dried Green Tea Based on the Combination of Mineral Elements and Stable Isotopes, columnId=1261343843585241413, journalTitle=Science and Technology of Food Industry, columnName=Analysis and Determination, runingTitle=null, highlight=null, articleAbstract=

To investigate the correlation between growing environment and stable isotopes and mineral elements in 80 Yunnan large-leaf sun-dried green tea samples (from 4 production areas: Ning'er County, Lianghe County, Simao District and Jinghong City, Yunnan Province), 24 trace elements, 14 rare earth elements and 5 stable isotopes were analyzed and determined by using Elemental Analyzer-Isotope Ratio Mass Spectrometry (EA-IRMS) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). To explore the feasibility of discriminating large-leaf sun-dried green tea from different geographical origins, multiple multivariate statistical methods were employed, including analysis of variance (ANOVA), principal component analysis (PCA), orthogonal partial least squares-discriminant analysis (OPLS-DA), and linear discriminant analysis (LDA). Tea from Lianghe County recorded a significantly higher total mineral element content compared to the other three regions (P<0.05). PCA extracted seven principal components with a total cumulative variance contribution rate of 80.831%. An OPLS-DA model provided effective differentiation of samples from the 4 different regions, from which 15 key variables with variable importance in projection (VIP) scores >1 were screened (δ2H, δ18O, Rb, Al, Tl, Cs, δ34S, Mn, Cu, Cd, Ga, Ba, Fe, As, Sr). Subsequently, these markers were subjected to Fisher's LDA. This model achieved 100.0% correct discrimination and a 92.5% cross-validation rate, demonstrating its robust capability for origin traceability of Yunnan large-leaf sun-dried green tea. This study demonstrated the feasibility of tracing the geographical origin of Yunnan large-leaf sun-dried green tea through mineral element and stable isotope analysis. The findings provided a research foundation for origin discrimination at a more accurate geographical scale and for the protection of geographical indication products in Yunnan.

, authors=Qixin ZOU1, 2, Xinyu LI1, Zeli CHEN1, Qian LI1, Benlin YIN1, Xuefeng WANG2, Xingyong LIU1, *, Jinliang SHAO1, *, authorsList=Qixin ZOU, Xinyu LI, Zeli CHEN, Qian LI, Benlin YIN, Xuefeng WANG, Xingyong LIU, Jinliang SHAO, authorCompany=null, correspAuthors=Xingyong LIU, Jinliang SHAO, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Science and Technology of Food Industry. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1320880712681632763, articleId=1320880709921780721, tenantId=1146029695717560320, journalId=1260987677001138203, language=CN, title=基于矿质元素与稳定同位素联用的云南晒青茶产地溯源, columnId=1261343846139572559, journalTitle=食品工业科技, columnName=分析检测, runingTitle=null, highlight=null, articleAbstract=

为研究云南大叶种晒青茶与产地环境的稳定同位素和矿质元素相关性,采用元素分析同位素质谱联用仪(Elemental Analysis-Isotope Ratio Mass Spectrometry,EA-IRMS)和电感耦合等离子体质谱仪(Inductively Coupled Plasma Mass Spectrometry,ICP-MS)对云南省宁洱县、梁河县、思茅区、景洪市四个产地80个茶叶样品的24种微量元素、14种稀土元素和5种稳定同位素进行了分析测定。结合单因素方差分析(analysis of variance,ANOVA)、主成分分析(principle components analysis,PCA)、正交偏最小二乘判别分析(orthogonal partial least squares-discriminant analysis,OPLS-DA)、线性判别分析(linear discriminant analysis,LDA)等多元统计分析方法探讨不同产地大叶种晒青茶判别的可行性。结果表明,梁河县的茶叶矿质元素总量显著高于其他三地(P<0.05)。PCA提取的7个主成分方差总贡献率为80.831%,基于OPLS-DA建立的判别模型,能够对4个县(市/区)茶叶的产地进行较好的区分,同时筛选出变量重要性投影(variable importance for the projection,VIP)值大于1的15个特征差异指标(δ2H、δ18O、Rb、Al、Tl、Cs、δ34S、Mn、Cu、Cd、Ga、Ba、Fe、As、Sr)并用于Fisher线性判别分析,构建的判别模型判别正确率为100.0%,交叉验证率为92.5%,基本实现了云南大叶种晒青茶的产地判别。本研究结果可通过矿质元素和稳定同位素对云南大叶种晒青茶产地溯源,为地理尺度更小的云南茶叶产地判别和地理标志产品保护提供研究思路。

, authors=邹启鑫1, 2, 李新宇1, 陈泽历1, 李倩1, 尹本林1, 王雪峰2, 刘兴勇1, *, 邵金良1, *, authorsList=邹启鑫, 李新宇, 陈泽历, 李倩, 尹本林, 王雪峰, 刘兴勇, 邵金良, authorCompany=null, correspAuthors=刘兴勇, 邵金良, authorNote=

邹启鑫(2002−),女,硕士研究生,研究方向:食品加工与安全,E-mail:

, correspAuthorsNote=
刘兴勇(1985−),男,硕士,助理研究员,研究方向:农产品质量安全,E-mail:。
邵金良(1979−),男,硕士,研究员,研究方向:农产品质量安全与品质评价,E-mail:。
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LWT, 2023, 181: 114742., articleTitle=null, refAbstract=null), Reference(id=1320881029708104587, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=37, rfOrder=55, authorNames=null, journalName=null, refType=null, unstructuredReference=KANRAR B, KUNDU S, KHAN P, et al. Elemental profiling for discrimination of geographical origin of tea (Camellia sinensis) in north-east region of India by ICP-MS coupled with chemometric techniques[J]. Food Chemistry Advances, 2022, 1: 100073., articleTitle=null, refAbstract=null), Reference(id=1320881029787796364, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=38, rfOrder=56, authorNames=null, journalName=null, refType=null, unstructuredReference=于寒冰, 郭阳, 李安, 等. 基于稳定同位素和元素技术的草莓产地溯源[J]. 食品安全质量检测学报, 2025, 16(3): 162−168. [YU Hanbing, GUO Yang, LI An, et al. Traceability of Fragariaananassa Duch. origin based on stable isotope and elemental technology[J]. Journal of Food Safety & Quality, 2025, 16(3): 162−168.], articleTitle=null, refAbstract=null), Reference(id=1320881029846516621, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=38, rfOrder=57, authorNames=null, journalName=null, refType=null, unstructuredReference=YU Hanbing, GUO Yang, LI An, et al. Traceability of Fragariaananassa Duch. origin based on stable isotope and elemental technology[J]. Journal of Food Safety & Quality, 2025, 16(3): 162−168., articleTitle=null, refAbstract=null), Reference(id=1320881029922014094, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=39, rfOrder=58, authorNames=null, journalName=null, refType=null, unstructuredReference=LIU Xiaohan, ZHAO Yan, MU Jian, et al. Determination of geographical origin of concentrated apple juice through analysis of stable isotopic and mineral elemental fingerprints: Preliminary results[J]. Journal of the Science of Food and Agriculture, 2021, 101(9): 3795−3803., articleTitle=null, refAbstract=null), Reference(id=1320881029980734351, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=40, rfOrder=59, authorNames=null, journalName=null, refType=null, unstructuredReference=刘宏程, 林昕, 和丽忠, 等. 基于稀土元素含量的普洱茶产地识别研究[J]. 茶叶科学, 2014, 34(5): 451−457. [LIU Hongcheng, LIN Xin, HE Lizhong, et al. The discrimination of Pu′er tea according to region of origin using the content of heavy rare-earth elements[J]. Journal of Tea Science, 2014, 34(5): 451−457.], articleTitle=null, refAbstract=null), Reference(id=1320881030060426128, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, doi=null, pmid=null, pmcid=null, year=null, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=40, rfOrder=60, authorNames=null, journalName=null, refType=null, unstructuredReference=LIU Hongcheng, LIN Xin, HE Lizhong, et al. The discrimination of Pu′er tea according to region of origin using the content of heavy rare-earth elements[J]. 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Related information of sample collection place

, figureFileSmall=null, figureFileBig=null, tableContent=
地区经度纬度
云南省普洱市宁洱哈尼族彝族自治县(以下简称宁洱县)100°42′ E-101°37′ E22°41′ N-23°36′ N
云南省德宏傣族景颇族自治州梁河县(以下简称梁河县)98°06′ E-98°34′ E24°31′ N-24°58′ N
云南省普洱市思茅区(以下简称思茅区)100°58′ E-101°50′ E22°27′ N-23°06′ N
云南省西双版纳傣族自治州傣族自治州景洪市(以下简称景洪市)100°25′ E-101°31′ E21°27′ N-22°36′ N
), ArticleFig(id=1320881017603343173, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表1, caption=

样品采集地相关信息

, figureFileSmall=null, figureFileBig=null, tableContent=
地区经度纬度
云南省普洱市宁洱哈尼族彝族自治县(以下简称宁洱县)100°42′ E-101°37′ E22°41′ N-23°36′ N
云南省德宏傣族景颇族自治州梁河县(以下简称梁河县)98°06′ E-98°34′ E24°31′ N-24°58′ N
云南省普洱市思茅区(以下简称思茅区)100°58′ E-101°50′ E22°27′ N-23°06′ N
云南省西双版纳傣族自治州傣族自治州景洪市(以下简称景洪市)100°25′ E-101°31′ E21°27′ N-22°36′ N
), ArticleFig(id=1320881017670452038, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=EN, label=Table 2, caption=

Trace element content (mg·kg−1)

, figureFileSmall=null, figureFileBig=null, tableContent=
元素种类宁洱县梁河县思茅区景洪市
Li0.082±0.001b0.169±0.001a0.040±0.004c0.064±0.003bc
Be0.004±0.000b0.010±0.000a未检出0.005±0.000b
Al1.890±0.101a1.642±0.128b0.715±0.141c0.815±0.019c
Ti6.495±1.852c14.151±1.470a3.950±0.505d8.625±0.522b
V0.083±0.001ab0.111±0.005a0.072±0.031bc0.043±0.003c
Cr0.185±0.007c0.926±0.064a0.118±0.001c0.422±0.074b
Mn1.410±0.206a1.098±0.071b0.495±0.064c0.710±0.040c
Fe78.70±8.833b115.816±6.550a28.495±1.640c87.790±3.568b
Co0.312±0.001a0.334±0.079a0.081±0.001b0.117±0.001b
Ni4.920±0.207b107.954±5.924a4.090±0.138b7.590±0.728b
Cu12.495±2.173b13.093±2.473b11.985±1.674b15.570±1.277a
Zn26.385±2.233b30.383±3.944ab32.920±3.496a35.010±4.146a
Ga1.680±0.175a1.392±0.042a0.730±0.075b0.720±0.007b
As0.029±0.008a0.016±0.009b0.012±0.002bc0.005±0.001c
Se未检出0.395±0.007a0.011±0.001b0.006±0.000b
Rb53.215±5.906c154.730±9.513a58.725±4.540c120.845±3.292b
Sr0.024±0.005a0.019±0.000a0.009±0.003b0.009±0.002b
Y0.300±0.006b0.470±0.043a0.029±0.002c0.079±0.009c
Mo未检出122.992±10.281a35.520±1.049b未检出
Cd0.056±0.004a0.029±0.006b0.026±0.001b0.025±0.003b
Cs0.578±0.009c1.127±0.074b0.315±0.024c1.627±0.030a
Ba30.605±3.889a25.803±2.275a12.565±2.931b14.840±3.183b
Tl0.054±0.003b0.134±0.000a0.029±0.001b0.172±0.015a
Pb0.096±0.003b0.202±0.002a0.021±0.002c0.031±0.008c
总含量219.63±10.282b593.009±14.729a190.953±9.565c295.12±8.671b
), ArticleFig(id=1320881017745949511, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表2, caption=

微量元素含量(mg·kg−1)

, figureFileSmall=null, figureFileBig=null, tableContent=
元素种类宁洱县梁河县思茅区景洪市
Li0.082±0.001b0.169±0.001a0.040±0.004c0.064±0.003bc
Be0.004±0.000b0.010±0.000a未检出0.005±0.000b
Al1.890±0.101a1.642±0.128b0.715±0.141c0.815±0.019c
Ti6.495±1.852c14.151±1.470a3.950±0.505d8.625±0.522b
V0.083±0.001ab0.111±0.005a0.072±0.031bc0.043±0.003c
Cr0.185±0.007c0.926±0.064a0.118±0.001c0.422±0.074b
Mn1.410±0.206a1.098±0.071b0.495±0.064c0.710±0.040c
Fe78.70±8.833b115.816±6.550a28.495±1.640c87.790±3.568b
Co0.312±0.001a0.334±0.079a0.081±0.001b0.117±0.001b
Ni4.920±0.207b107.954±5.924a4.090±0.138b7.590±0.728b
Cu12.495±2.173b13.093±2.473b11.985±1.674b15.570±1.277a
Zn26.385±2.233b30.383±3.944ab32.920±3.496a35.010±4.146a
Ga1.680±0.175a1.392±0.042a0.730±0.075b0.720±0.007b
As0.029±0.008a0.016±0.009b0.012±0.002bc0.005±0.001c
Se未检出0.395±0.007a0.011±0.001b0.006±0.000b
Rb53.215±5.906c154.730±9.513a58.725±4.540c120.845±3.292b
Sr0.024±0.005a0.019±0.000a0.009±0.003b0.009±0.002b
Y0.300±0.006b0.470±0.043a0.029±0.002c0.079±0.009c
Mo未检出122.992±10.281a35.520±1.049b未检出
Cd0.056±0.004a0.029±0.006b0.026±0.001b0.025±0.003b
Cs0.578±0.009c1.127±0.074b0.315±0.024c1.627±0.030a
Ba30.605±3.889a25.803±2.275a12.565±2.931b14.840±3.183b
Tl0.054±0.003b0.134±0.000a0.029±0.001b0.172±0.015a
Pb0.096±0.003b0.202±0.002a0.021±0.002c0.031±0.008c
总含量219.63±10.282b593.009±14.729a190.953±9.565c295.12±8.671b
), ArticleFig(id=1320881017813058376, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=EN, label=Table 3, caption=

Rare earth element content (μg·kg−1)

, figureFileSmall=null, figureFileBig=null, tableContent=
元素种类宁洱县梁河县思茅区景洪市
La189.425±8.817b671.390±15.657a81.695±5.603c78.940±5.295c
Ce332.850±14.490b710.786±24.382a148.68±7.037c151.260±7.399c
Pr46.455±2.780b119.864±7.972a14.970±2.183c13.710±1.767c
Nd189.925±9.883b461.613±20.958a61.105±1.926c56.145±4.085c
Sm48.005±1.456b93.454±6.762a10.985±0.803c1.975±0.004c
Eu12.520±3.850b17.958±2.002a3.140±0.252c2.160±0.109c
Gd55.005±6.941b73.081±3.546a13.235±2.619c13.775±2.469c
Tb8.325±0.709b14.368±3.504a1.765±0.795c0.550±0.006c
Dy51.850±7.284b80.934±7.644a10.880±1.515c17.095±1.842c
Ho11.105±1.749b18.621±3.702a2.105±0.021c3.715±0.451c
Er30.345±2.256b58.453±2.830a6.175±0.652c9.095±2.628c
Tm4.720±0.595b10.063±2.806a0.995±0.107c1.860±0.002c
Yb47.920±0.943b87.221±4.345a6.960±1.106c10.635±1.903c
Lu6.700±0.838b13.173±4.267a1.085±0.008c2.310±0.084c
总含量1035.150±26.082b2430.979±47.156a363.775±12.793c363.225±16.731c
), ArticleFig(id=1320881017880167241, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表3, caption=

稀土元素含量(μg·kg−1)

, figureFileSmall=null, figureFileBig=null, tableContent=
元素种类宁洱县梁河县思茅区景洪市
La189.425±8.817b671.390±15.657a81.695±5.603c78.940±5.295c
Ce332.850±14.490b710.786±24.382a148.68±7.037c151.260±7.399c
Pr46.455±2.780b119.864±7.972a14.970±2.183c13.710±1.767c
Nd189.925±9.883b461.613±20.958a61.105±1.926c56.145±4.085c
Sm48.005±1.456b93.454±6.762a10.985±0.803c1.975±0.004c
Eu12.520±3.850b17.958±2.002a3.140±0.252c2.160±0.109c
Gd55.005±6.941b73.081±3.546a13.235±2.619c13.775±2.469c
Tb8.325±0.709b14.368±3.504a1.765±0.795c0.550±0.006c
Dy51.850±7.284b80.934±7.644a10.880±1.515c17.095±1.842c
Ho11.105±1.749b18.621±3.702a2.105±0.021c3.715±0.451c
Er30.345±2.256b58.453±2.830a6.175±0.652c9.095±2.628c
Tm4.720±0.595b10.063±2.806a0.995±0.107c1.860±0.002c
Yb47.920±0.943b87.221±4.345a6.960±1.106c10.635±1.903c
Lu6.700±0.838b13.173±4.267a1.085±0.008c2.310±0.084c
总含量1035.150±26.082b2430.979±47.156a363.775±12.793c363.225±16.731c
), ArticleFig(id=1320881017972441930, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=EN, label=Table 4, caption=

Stable isotope ratio (‰)

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同位素
种类
宁洱县梁河县思茅区景洪市
δ13C−26.375±0.663b−27.010±0.828c−25.700±0.993a−26.310±0.442b
δ15N3.505±0.585a2.355±0.832b3.290±0.795a3.255±0.398a
δ2H−49.250±3.129c−45.570±3.437b−29.925±3.628a−68.570±3.673d
δ18O21.870±0.296c22.910±0.757b23.450±0.325a18.355±0.296d
δ34S7.815±0.118a4.485±0.811b7.235±0.286a7.530±0.310a
), ArticleFig(id=1320881018039550795, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表4, caption=

稳定同位素比值(‰)

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同位素
种类
宁洱县梁河县思茅区景洪市
δ13C−26.375±0.663b−27.010±0.828c−25.700±0.993a−26.310±0.442b
δ15N3.505±0.585a2.355±0.832b3.290±0.795a3.255±0.398a
δ2H−49.250±3.129c−45.570±3.437b−29.925±3.628a−68.570±3.673d
δ18O21.870±0.296c22.910±0.757b23.450±0.325a18.355±0.296d
δ34S7.815±0.118a4.485±0.811b7.235±0.286a7.530±0.310a
), ArticleFig(id=1320881018140214092, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=EN, label=Table 5, caption=

Results of PCA

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元素主成分1主成分2主成分3主成分4主成分5主成分6主成分7
Li0.1510.1420.1080.1990.025−0.173−0.010
Be0.1020.136−0.0390.095−0.1410.0920.136
Al0.164−0.162−0.1760.114−0.0370.092−0.056
Ti0.1420.2670.0600.165−0.015−0.225−0.001
V0.0800.1000.2410.409−0.064−0.172−0.055
Cr0.1350.2160.1190.0490.237−0.0400.039
Mn0.105−0.072−0.1150.2630.1410.057−0.183
Fe0.1300.259−0.0540.2580.019−0.142−0.121
Co0.153−0.114−0.1620.0020.1620.029−0.138
Ni0.0770.110.201−0.014−0.0420.444−0.070
Cu−0.0150.225−0.217−0.0500.3480.097−0.043
Zn−0.0450.1640.1470.0150.5050.1940.144
Ga0.126−0.170−0.2170.1970.036−0.0010.356
As0.059−0.0870.0620.387−0.037−0.104−0.162
Se0.1140.0160.019−0.0980.379−0.1670.207
Rb0.0960.3500.067−0.042−0.0330.029−0.110
Sr0.121−0.125−0.1460.2180.0500.0870.241
Y0.218−0.009−0.0190.014−0.0250.128−0.048
Mo0.0600.1010.250−0.0010.2570.3860.020
Cd0.046−0.166−0.1720.1800.1190.243−0.340
Cs0.0240.292−0.236−0.104−0.1820.0610.074
Ba0.127−0.145−0.2460.1920.030−0.0040.363
Tl0.0340.308−0.223−0.054−0.200−0.0400.145
Pb0.1720.1320.1480.217−0.015−0.050−0.071
La0.203−0.0020.036−0.1740.132−0.1550.110
Ce0.212−0.0030.024−0.1160.010−0.1110.035
Pr0.214−0.0240.026−0.1320.081−0.1100.087
Nd0.215−0.0250.024−0.1160.078−0.0940.081
Sm0.213−0.0810.023−0.0940.0100.0450.062
Eu0.204−0.143−0.062−0.0790.067−0.0410.071
Gd0.212−0.098−0.0440.0110.0180.017−0.049
Tb0.219−0.0700.043−0.061−0.0130.087−0.058
Dy0.220−0.033−0.031−0.050−0.0850.090−0.057
Ho0.221−0.017−0.024−0.062−0.0780.078−0.075
Er0.2190.0030.024−0.090−0.1050.093−0.065
Tm0.2140.0290.014−0.103−0.1390.0870.000
Yb0.2120.0020.028−0.063−0.1520.152−0.078
Lu0.2080.0230.014−0.094−0.1470.150−0.058
δ13C−0.113−0.0120.1610.110−0.1050.1760.301
δ15N−0.074−0.153−0.174−0.0320.222−0.100−0.367
δ2H0.011−0.2380.4150.016−0.0370.0270.072
δ18O0.076−0.2710.354−0.025−0.033−0.1530.037
δ34S−0.134−0.003−0.0490.282−0.0460.3380.189
方差贡献率43.87911.2577.1766.54868.8603.9883.261
累计贡献率43.87955.13662.3124.72273.58277.57080.831
), ArticleFig(id=1320881018232488781, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表5, caption=

PCA结果

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元素主成分1主成分2主成分3主成分4主成分5主成分6主成分7
Li0.1510.1420.1080.1990.025−0.173−0.010
Be0.1020.136−0.0390.095−0.1410.0920.136
Al0.164−0.162−0.1760.114−0.0370.092−0.056
Ti0.1420.2670.0600.165−0.015−0.225−0.001
V0.0800.1000.2410.409−0.064−0.172−0.055
Cr0.1350.2160.1190.0490.237−0.0400.039
Mn0.105−0.072−0.1150.2630.1410.057−0.183
Fe0.1300.259−0.0540.2580.019−0.142−0.121
Co0.153−0.114−0.1620.0020.1620.029−0.138
Ni0.0770.110.201−0.014−0.0420.444−0.070
Cu−0.0150.225−0.217−0.0500.3480.097−0.043
Zn−0.0450.1640.1470.0150.5050.1940.144
Ga0.126−0.170−0.2170.1970.036−0.0010.356
As0.059−0.0870.0620.387−0.037−0.104−0.162
Se0.1140.0160.019−0.0980.379−0.1670.207
Rb0.0960.3500.067−0.042−0.0330.029−0.110
Sr0.121−0.125−0.1460.2180.0500.0870.241
Y0.218−0.009−0.0190.014−0.0250.128−0.048
Mo0.0600.1010.250−0.0010.2570.3860.020
Cd0.046−0.166−0.1720.1800.1190.243−0.340
Cs0.0240.292−0.236−0.104−0.1820.0610.074
Ba0.127−0.145−0.2460.1920.030−0.0040.363
Tl0.0340.308−0.223−0.054−0.200−0.0400.145
Pb0.1720.1320.1480.217−0.015−0.050−0.071
La0.203−0.0020.036−0.1740.132−0.1550.110
Ce0.212−0.0030.024−0.1160.010−0.1110.035
Pr0.214−0.0240.026−0.1320.081−0.1100.087
Nd0.215−0.0250.024−0.1160.078−0.0940.081
Sm0.213−0.0810.023−0.0940.0100.0450.062
Eu0.204−0.143−0.062−0.0790.067−0.0410.071
Gd0.212−0.098−0.0440.0110.0180.017−0.049
Tb0.219−0.0700.043−0.061−0.0130.087−0.058
Dy0.220−0.033−0.031−0.050−0.0850.090−0.057
Ho0.221−0.017−0.024−0.062−0.0780.078−0.075
Er0.2190.0030.024−0.090−0.1050.093−0.065
Tm0.2140.0290.014−0.103−0.1390.0870.000
Yb0.2120.0020.028−0.063−0.1520.152−0.078
Lu0.2080.0230.014−0.094−0.1470.150−0.058
δ13C−0.113−0.0120.1610.110−0.1050.1760.301
δ15N−0.074−0.153−0.174−0.0320.222−0.100−0.367
δ2H0.011−0.2380.4150.016−0.0370.0270.072
δ18O0.076−0.2710.354−0.025−0.033−0.1530.037
δ34S−0.134−0.003−0.0490.282−0.0460.3380.189
方差贡献率43.87911.2577.1766.54868.8603.9883.261
累计贡献率43.87955.13662.3124.72273.58277.57080.831
), ArticleFig(id=1320881018337346382, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=EN, label=Table 6, caption=

K-NN and SVM prediction results

, figureFileSmall=null, figureFileBig=null, tableContent=
模型宁洱县梁河县思茅区景洪市准确度
(%)
总体精度
(%)
SVM
预测
宁洱县1505075
梁河县02000100
思茅区00200100
景洪市0002010093.75
K-NN
预测
宁洱县20000100
梁河县02000100
思茅区00200100
景洪市00020100100
), ArticleFig(id=1320881018412843855, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表6, caption=

K-NN和SVM预测结果

, figureFileSmall=null, figureFileBig=null, tableContent=
模型宁洱县梁河县思茅区景洪市准确度
(%)
总体精度
(%)
SVM
预测
宁洱县1505075
梁河县02000100
思茅区00200100
景洪市0002010093.75
K-NN
预测
宁洱县20000100
梁河县02000100
思茅区00200100
景洪市00020100100
), ArticleFig(id=1320881018484147024, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=EN, label=Table 7, caption=

Centroids function

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产地123
宁洱县1.2171.1773.784
梁河县2.5493.319−2.349
思茅区8.260−3.153−0.783
景洪市−12.026−1.343−0.652
), ArticleFig(id=1320881018551255889, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表7, caption=

组质心函数

, figureFileSmall=null, figureFileBig=null, tableContent=
产地123
宁洱县1.2171.1773.784
梁河县2.5493.319−2.349
思茅区8.260−3.153−0.783
景洪市−12.026−1.343−0.652
), ArticleFig(id=1320881018626753362, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=EN, label=Table 8, caption=

Results of discriminant classification

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地区预测组成员总计
宁洱县梁河县思茅区景洪市
原始计数(个)宁洱县2000020
梁河县0200020
思茅区0020020
景洪市0002020
判别率(%)宁洱县100000100
梁河县010000100
思茅区001000100
景洪市000100100
交叉验证计数(个)宁洱县1820020
梁河县4160020
思茅区0020020
景洪市0002020
判别率(%)宁洱县901000100
梁河县208000100
思茅区001000100
景洪市000100100
), ArticleFig(id=1320881018698056531, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320880709921780721, language=CN, label=表8, caption=

判别分类结果

, figureFileSmall=null, figureFileBig=null, tableContent=
地区预测组成员总计
宁洱县梁河县思茅区景洪市
原始计数(个)宁洱县2000020
梁河县0200020
思茅区0020020
景洪市0002020
判别率(%)宁洱县100000100
梁河县010000100
思茅区001000100
景洪市000100100
交叉验证计数(个)宁洱县1820020
梁河县4160020
思茅区0020020
景洪市0002020
判别率(%)宁洱县901000100
梁河县208000100
思茅区001000100
景洪市000100100
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基于矿质元素与稳定同位素联用的云南晒青茶产地溯源
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邹启鑫 1, 2 , 李新宇 1 , 陈泽历 1 , 李倩 1 , 尹本林 1 , 王雪峰 2 , 刘兴勇 1, * , 邵金良 1, *
食品工业科技 | 分析检测 2026,47(17): 386-394
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食品工业科技 |分析检测 2026 , 47 (17) : 386 -394
基于矿质元素与稳定同位素联用的云南晒青茶产地溯源
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邹启鑫1, 2 , 李新宇1, 陈泽历1, 李倩1, 尹本林1, 王雪峰2, 刘兴勇1, * , 邵金良1, *
作者信息
  • 1云南省农业科学院质量标准与检测技术研究所,云南昆明 650205
  • 2云南农业大学食品科学技术学院,云南昆明 650201
通讯作者:
刘兴勇(1985−),男,硕士,助理研究员,研究方向:农产品质量安全,E-mail:。
邵金良(1979−),男,硕士,研究员,研究方向:农产品质量安全与品质评价,E-mail:。
作者简介:

邹启鑫(2002−),女,硕士研究生,研究方向:食品加工与安全,E-mail:

Geographical Traceability of Yunnan Sun-dried Green Tea Based on the Combination of Mineral Elements and Stable Isotopes
Qixin ZOU1, 2 , Xinyu LI1, Zeli CHEN1, Qian LI1, Benlin YIN1, Xuefeng WANG2, Xingyong LIU1, * , Jinliang SHAO1, *
Affiliations
  • 1Institute of Agriculture Quality Standards & Testing Technique, Yunnan Academy of Agricultural Science, Kunming 650205, China
  • 2Faculty of Food Science and Technology, Yunnan Agricultural University, Kunming 650201, China
出版时间: 2026-09-01 doi: 10.13386/j.issn1002-0306.2025080105
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为研究云南大叶种晒青茶与产地环境的稳定同位素和矿质元素相关性,采用元素分析同位素质谱联用仪(Elemental Analysis-Isotope Ratio Mass Spectrometry,EA-IRMS)和电感耦合等离子体质谱仪(Inductively Coupled Plasma Mass Spectrometry,ICP-MS)对云南省宁洱县、梁河县、思茅区、景洪市四个产地80个茶叶样品的24种微量元素、14种稀土元素和5种稳定同位素进行了分析测定。结合单因素方差分析(analysis of variance,ANOVA)、主成分分析(principle components analysis,PCA)、正交偏最小二乘判别分析(orthogonal partial least squares-discriminant analysis,OPLS-DA)、线性判别分析(linear discriminant analysis,LDA)等多元统计分析方法探讨不同产地大叶种晒青茶判别的可行性。结果表明,梁河县的茶叶矿质元素总量显著高于其他三地(P<0.05)。PCA提取的7个主成分方差总贡献率为80.831%,基于OPLS-DA建立的判别模型,能够对4个县(市/区)茶叶的产地进行较好的区分,同时筛选出变量重要性投影(variable importance for the projection,VIP)值大于1的15个特征差异指标(δ2H、δ18O、Rb、Al、Tl、Cs、δ34S、Mn、Cu、Cd、Ga、Ba、Fe、As、Sr)并用于Fisher线性判别分析,构建的判别模型判别正确率为100.0%,交叉验证率为92.5%,基本实现了云南大叶种晒青茶的产地判别。本研究结果可通过矿质元素和稳定同位素对云南大叶种晒青茶产地溯源,为地理尺度更小的云南茶叶产地判别和地理标志产品保护提供研究思路。

大叶种晒青茶  /  矿质元素  /  稳定同位素  /  主成分分析  /  判别分析  /  产地溯源

To investigate the correlation between growing environment and stable isotopes and mineral elements in 80 Yunnan large-leaf sun-dried green tea samples (from 4 production areas: Ning'er County, Lianghe County, Simao District and Jinghong City, Yunnan Province), 24 trace elements, 14 rare earth elements and 5 stable isotopes were analyzed and determined by using Elemental Analyzer-Isotope Ratio Mass Spectrometry (EA-IRMS) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). To explore the feasibility of discriminating large-leaf sun-dried green tea from different geographical origins, multiple multivariate statistical methods were employed, including analysis of variance (ANOVA), principal component analysis (PCA), orthogonal partial least squares-discriminant analysis (OPLS-DA), and linear discriminant analysis (LDA). Tea from Lianghe County recorded a significantly higher total mineral element content compared to the other three regions (P<0.05). PCA extracted seven principal components with a total cumulative variance contribution rate of 80.831%. An OPLS-DA model provided effective differentiation of samples from the 4 different regions, from which 15 key variables with variable importance in projection (VIP) scores >1 were screened (δ2H, δ18O, Rb, Al, Tl, Cs, δ34S, Mn, Cu, Cd, Ga, Ba, Fe, As, Sr). Subsequently, these markers were subjected to Fisher's LDA. This model achieved 100.0% correct discrimination and a 92.5% cross-validation rate, demonstrating its robust capability for origin traceability of Yunnan large-leaf sun-dried green tea. This study demonstrated the feasibility of tracing the geographical origin of Yunnan large-leaf sun-dried green tea through mineral element and stable isotope analysis. The findings provided a research foundation for origin discrimination at a more accurate geographical scale and for the protection of geographical indication products in Yunnan.

large-leaved sun-dried tea  /  mineral elements  /  stable isotope  /  principal component analysis  /  discriminant analysis  /  geographical origin traceability
邹启鑫, 李新宇, 陈泽历, 李倩, 尹本林, 王雪峰, 刘兴勇, 邵金良. 基于矿质元素与稳定同位素联用的云南晒青茶产地溯源. 食品工业科技, 2026 , 47 (17) : 386 -394 . DOI: 10.13386/j.issn1002-0306.2025080105
Qixin ZOU, Xinyu LI, Zeli CHEN, Qian LI, Benlin YIN, Xuefeng WANG, Xingyong LIU, Jinliang SHAO. Geographical Traceability of Yunnan Sun-dried Green Tea Based on the Combination of Mineral Elements and Stable Isotopes[J]. Science and Technology of Food Industry, 2026 , 47 (17) : 386 -394 . DOI: 10.13386/j.issn1002-0306.2025080105
茶原产于中国,如今已成为消费量仅次于水的全球性饮料[1]。云南凭借其独特的自然生态条件,已成为我国主要茶叶产区之一。云南大叶种晒青茶富含茶多酚、生物碱、茶色素及黄酮醇等多种生物活性成分[2],具有抗炎[3]、抗氧化[4]、降血糖[5]、降血脂[6]及预防心血管疾病[7]等生理功效。该地区立体复杂的气候特征,包括温差、光照、水分和微域环境,是形成茶叶醇厚滋味、馥郁香气以及内含物质丰富且区域风味差异显著的关键自然因素[8]。云南大叶种茶叶的品质与风味与其生长的地域环境密切相关,茶树通过根系吸收土壤中的矿质元素并积累于叶片中,形成具有产地特异性的“元素指纹”,从而直接关联茶叶的地理来源及其核心价值。然而,当前市场上存在将非核心产区茶叶冒充地理标志产品的现象,部分经营者将劣质或异地茶叶伪装成云南普洱茶等知名品类销售,严重损害了云南大叶种茶的品牌信誉,也侵害了消费者与正规企业的合法权益。因此,开展针对云南大叶种茶的矿质元素产地溯源研究具有重要现实意义。通过精准识别不同产地茶叶中矿质元素的差异,构建稳定、可靠的产地判别模型,不仅有助于保护普洱茶等地理标志产品的特色,也对规范市场秩序、促进产业健康发展具有重要意义。
近年来,基于矿质元素与稳定同位素特征的产地溯源技术已成为保护地理标志农产品的重要手段[9−13]。矿质元素作为土壤-植物系统的天然标识物,其在茶叶中的积累模式可反映种植区的地球化学背景[13],在茶叶生长和加工过程中具有较好的稳定性,并能提供多维度的元素组成信息[14]。稳定同位素作为“环境指纹”,与区域土壤、大气降水及水源等环境因素密切相关,且受人为干扰较小,有助于提升判别模型的准确性与稳定性[15]。矿质元素主要反映地质背景,同位素则更敏感于气候条件;二者结合可构建互补型溯源体系[16]。例如,邓诗意等[17]通过测定板栗的稳定同位素与矿物元素构建产地判别模型,对10个产地的板栗样本实现了OPLS-DA模型交叉验证判别率100%。类似方法在蜂蜜[18]、陈皮[19]等初加工或未加工的地理标志农产品溯源中也取得了较高准确率。
晒青茶作为普洱茶的关键原料,其产地来源直接影响普洱茶的品质与市场价值。目前相关研究多基于挥发性风味物质[20]或香气成分分析[21]进行鉴别,然而茶叶的干燥工艺[22]、发酵条件[23]等因素会影响香气组成,因而存在一定局限性。相比之下,将矿质元素与稳定同位素相结合用于云南晒青茶产地溯源的研究仍较为缺乏。
梁河大叶种茶以清冽花香,彰显边缘产区的独特风采;思茅大叶种茶以醇和饱满,成就现代普洱的品质典范;宁洱大叶种茶以苦底回甘,承载古府茶韵的深厚底蕴;景洪大叶种茶以浓强霸气,奠定越陈越香的核心基石。为此,本研究基于地理-矿质元素对应原则,自北向南采集云南省这4个产区(梁河、思茅、宁洱、景洪)的大叶种晒青茶样品80份,测定其矿质元素含量与稳定同位素组成,共获取43项指标数据,结合主成分分析与判别分析等化学计量学方法筛选特征指标,构建产地判别模型。本研究不仅能为产地溯源提供科学依据,而且可对晒青茶的元素指纹图谱提供基础数据。
茶叶样品 于2022年4~7月采集于云南省普洱市宁洱哈尼族彝族自治县(以下简称宁洱县)、云南省德宏傣族景颇族自治州梁河县(以下简称梁河县)、云南省普洱市思茅区(以下简称思茅区)、云南省西双版纳傣族自治州景洪市(以下简称景洪市)的大叶种茶鲜叶(一芽三叶或一芽四叶),每个产地20份,共计80份样品。新鲜茶叶统一经蒸汽杀青后,于自然光照下晒干备用。采样地点见表1。Li、Be、Al、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、As、Pb、Sr、Tl、Ba、Y、Cs、Cd的多元素标准溶液(100 μg·mL−1)(批号GNM-M324760-2013),La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu的多元素标准溶液(100 μg·mL−1)(批号GNM-M160181-2013),单元素标准溶液Se(批号GNM-SCS-011-2013)、Rb(批号GNM-SRB-002-2013)、Mo(批号GNM-SMO-002-2013)(均为1000 μg·mL−1) 均购自国家有色金属及电子材料分析测试中心。
ICPMS/MS 8900型电感耦合等离子体质谱仪 美国Agilent公司;Isotope cube元素分析仪、Biovision气体同位素质谱仪、PYRO-cube元素分析仪 德国Elementar公司。
先将少量干燥样品磨碎,过100目筛后置于烘箱中干燥,冷却至室温后置于干燥器内保存,待测。进行多元素检测前,需将样品和标准物质一起在检测环境下平衡72 h。
参照LIU等[24]的方法并稍作修改。采用ICP-MS对待测液进行多元素含量的测定。精密称取样品0.1 g,置于密封高压消解管中。用几滴超纯水湿润后,加5 mL硝酸,浸泡0.5 h后,加入2 mL过氧化氢,待样品被酸液充分浸润后,盖紧罐盖,并将消解罐安装好,放入电热恒温鼓风干燥箱中,于170 ℃下平衡24 h进行密闭消解。样品消解完成之后,取出消解罐置于通风橱中降至室温。取出内罐,用2%硝酸溶液将消解液转移至50 mL刻度容量瓶中定容,摇匀,静置,溶液澄清后待测。
ICP-MS条件:高频等离子体发射功率1550 W;载气为高纯氩气;同心雾化器;载气流速0.85 L·min−1;气补偿气流量0.15 L·min−1;采样深度9.5 mm;蠕动泵0.3 r·min−1。
参照CHEN等[25]的方法并稍作修改。
δ13C、δ15N和δ34S测定:称取10.0 mg样品用锡箔杯包好后放置于Isotope cube元素分析仪样品盘中,样品中的碳元素、氮元素和硫元素转化为纯净的CO2、N2和SO2气体后,进入Biovision气体同位素质谱仪检测。元素分析具体条件:燃烧管主要填料为WO3,1150 ℃,还原管填料为Cu,850 ℃,高纯氦气(99.999%)作为载气。同位素质谱的主要条件:CO2阱电流100 μA,N2阱电流400 μA,SO2阱电流600 μA。采用CentrION对CO2气体进行稀释,实现三种气体的同时测定。
δ2H和δ18O测定:称取0.5 mg样品放入PYRO-cube元素分析仪样品盘中,样品中的氢元素和氧元素转化为纯净的H2和CO气体后,进入Isoprime 100气体同位素质谱仪进行检测。元素分析主要条件:裂解管主要填料为碳玻璃,1450 ℃,高纯氦气(99.999%)作为载气。同位素质谱的主要条件:CO阱电流200 μA,H2阱电流400 μA。采用稀释器对CO气体进行稀释,实现两种气体的同时测定。
所述δ13C、δ15N、δ2H、δ18O和δ34S稳定同位素比值计算公式为:
$\rm {{\delta}}\mathrm{E(\text{‰})=(R_{样品}/R_{标准}-1)\times 1000} $
式中,E为目标元素同位素;R样品为所测样品中重同位素与轻同位素丰度比(13C/12C、15N/14N、34S/32S、18O/16O和2H/1H);R标准为标准样品中重同位素与轻同位素丰度比。
采用SPSS29.0.1.0对数据进行单因素方差、多重比较(事后比较、LSD和邓肯、描述和方差齐性检验)和判别分析,利用SIMCA14.1.0进行偏最小二乘判别分析,用OriginPro2024b进行主成分分析和相关性分析。
不同产地大叶种晒青茶中微量元素含量见表2。不同产地茶叶中的24种微量元素含量在各产地间具有显著差异性(P<0.05)。其中,梁河县茶叶中微量元素的总含量最高,景洪市和宁洱县次之,思茅区最低;梁河县茶叶中11种(Li、Be、Ti等)微量元素含量显著高于其他3个产地,且Fe、Ni、Rb、Mo含量相对较高(P<0.05);宁洱县的4种(Al、Mn、As、Cd)微量元素含量较其他3个产地显著提高(P<0.05);Cu、Zn和Cs含量在景洪市较高,思茅区茶叶中微量元素的含量均较低。不同产地的大叶种晒青茶中微量元素的含量不同,可能是受到各地区的土壤条件影响[26]。
不同产地大叶种晒青茶中的稀土元素含量见表3,结果表明:4个产地茶叶样品的稀土元素含量存在差异。梁河县茶叶中稀土元素的总含量最高,宁洱县次之,思茅区和景洪市产地的含量较低,且梁河县茶叶的14种稀土元素含量显著高于其他3个产地(P<0.05)。思茅区和景洪市两个产地茶叶样品中的稀土元素含量差异很小,可能是由于两地在地理位置上相邻,土壤中的矿质元素组成有一定相似性[27]。
对4个产地大叶种晒青茶的稳定同位素比值进行分析,如表4所示:不同产地的δ13C值在−27.01‰~−25.7‰,思茅区茶叶中δ13C值最高,梁河县最低,可能是受到不同气候和环境因子的影响。δ15N值为2.355‰~3.505‰,宁洱县、思茅区和景洪市茶叶中的δ15N值均显著高于梁河县(P<0.05),原因可能是δ15N的组成差异受地理位置的影响。δ2H值为−68.57‰~−29.925‰,δ18O值为18.355‰~23.45‰,4个产地茶叶中δ2H值和δ18O值均具有显著差异(P<0.05),其中,思茅区茶叶中δ2H值和δ18O值均高于其他3地,可能是受该地温和稳定、干湿分明、垂直差异显著气候的影响;δ34S值为4.485‰~7.815‰,梁河县茶叶中δ34S值显著低于其他产地(P<0.05),含量的差异主要由于不同产地间土壤母质的差异导致[28−29]。
主成分分析的前提是假设原始数据变量之间具有较强的线性相关性,因此对测量质量分量之间的相关性进行了分析[30]。将43个云南大叶种晒青茶测定指标进行皮尔逊(Person)相关性热图分析,由于数据量较大,故将P值设置为0.001极显著范围。结果如图1所示,大多数稀土元素彼此呈正相关,而稳定同位素与大多数微量元素和部分稀土元素呈负相关,各质量因子间的相关性存在较多的重叠,需要进一步进行主成分分析。
PCA是通过对数据进行降维的方法,将多个变量转为少数几个综合变量的多元统计分析方法,作为一种无监督模式的判别方法[31]。为了判别造成不同产地云南大叶种晒青茶存在差异的元素指标,用PCA对茶叶样品测定的43个指标进行初步分析是否存在差异性。PCA结果如表5所示,根据主成分累积方差贡献率不低于80%的原则,提取前7个主成分指标,前7个主成分方差累计贡献率为80.831%,代表了43个指标大部分信息,反映4个产地云南大叶种晒青茶的元素差异。
根据表5,利用前2个主成分做得分散点图(图2),可以看出4个产地的茶叶在图中虽然在一定程度上实现了初步分类,但分离度较差,梁河县和宁洱县产地样品的组内较松散,干扰较多,聚集度低,分类效果不理想,需进一步使用有监督模式的判别模型优化分析。
为了进一步明确造成云南4个产地大叶种晒青茶存在差异的物质,采用OPLS-DA进一步处理数据,分别对与因变量相关和正交的预测器变化进行建模。从得分图横坐标的方向可以看出组间的差异,从纵坐标上看出各组内的差异,两组数据在横坐标上距离越远,组间差异越大,在纵坐标上距离越远,组内差距越大[32]。由图3A可以看出不同产地样品差异明显,并且所有样本数均在95%的置信区间内没有明显异常值,说明试验样本数据都在正常值范围内。VIP值是OPLS-DA模型筛选差异成分的主要指标之一,VIP值越大代表该物质对于区分组间差异贡献越大,通常将VIP值>1的指标作为判定差异的主要指标[33]。由图3B可以看出,VIP值>1的指标由大到小依次为δ2H、δ18O、Rb、Al、Tl、Cs、δ34S、Mn、Cu、Cd、Ga、Ba、Fe、As、Sr这15个指标可作为导致4个产地云南大叶种晒青茶存在差异的主要标志性成分。为了探究OPLS-DA模型是否出现过拟合,需要对模型进行200次交叉置换检验[34],结果如图3C所示,Q2与Y轴上的截距小于0,说明没有出现过拟合,该模型的验证有效。
支持向量机(support vector machine,SVM)是一种经典的监督学习分类算法,核心目标是在高维特征空间中找到一条“最优分类超平面”,使超平面到两侧最近样本(即“支持向量”)的距离(间隔)最大化,从而实现对未知样本的精准分类[35]。k-最近邻法(k-nearest neighbors,k-NN)基于“相似的样本会聚集在同一区域”的直观假设——通过计算未知样本与已知样本的“距离相似性”,筛选出最接近的k个“邻居”,并以邻居的类别投票结果确定未知样本的类别,在小样本、低维数据或需快速验证的场景中应用广泛[36]。利用SVM和k-NN对80个茶叶样品进行预测分类,结果如表6所示,SVM的分类正确率为93.75%,k-NN的分类正确率为100%,模型预测的准确率均较高。相同模型预测下,Kanrar等[37]对来自8个地区的茶叶样本中67种元素进行分析,利用OPLS-DA模型实现了产地正确分类率100%,SVM模型的分类正确率分别为99.4%。本研究中SVM模型的判别准确率为93.75%,相较于上述结果略低,推测可能与部分采样区域地理位置相邻有关。
线性判别分析(linear discriminant analysis,LDA)是一种判别样本所属类别的统计方法,其可利用样本间的相关性建立判别模型而对未知样本分类,还可利用交叉验证把除某一个样本之外的其余样本作为训练集,建立判别函数对该样本进行判别,从而检验判别模型的稳定性[38−39]。为了验证不同模型分析结果的一致性,并验证差异物质的判别效果,根据OPLS-DA中VIP值>1的15个特征差异成分作为自变量,用Fisher函数建立云南大叶种晒青茶的产地判别模型。经分析后得到3个组质心函数(表7)和3个判别函数方程,见公式(1)~(3),其中Y1~Y3分别代表第1~3典型判别函数,X代表筛选出的15种特征差异物。
$ \begin{split} & \mathrm{Y1=-34.597-0.115X}_{\mathrm{Al}}\mathrm{+0.132X}_{\mathrm{Mn}}\mathrm{-0.013X}_{\mathrm{Fe}}- \\ & \quad\quad\; \; \mathrm{0.118X}_{\mathrm{Cu}}\mathrm{+6.379X}_{\mathrm{Ga}}\mathrm{+21.366X}_{\mathrm{As}}\mathrm{+0.349X}_{\mathrm{Sr}}+ \\ & \quad\quad\; \; \mathrm{1.290X}_{\mathrm{Cd}}-\mathrm{0.322X}_{\mathrm{Ba}}\mathrm{+0.041X}_{\mathrm{Tl}}\mathrm{+0.190X}_{\delta^2\mathrm{H}}+ \\ & \quad\quad\; \; \mathrm{2.087X}_{\delta^{18}\mathrm{O}}\mathrm{+0.078X}_{\delta^{\mathit{\mathrm{34}}}\mathrm{S}}-\mathrm{0.139X}_{\mathrm{Cs}}\end{split} $
$ \begin{split} & \mathrm{Y2=-13.171+1.872X}_{\mathrm{Al}}\mathrm{+0.576X}_{\mathrm{Mn}}\mathrm{-0.019X}_{\mathrm{Fe}}- \\ & \quad\quad\; \; \mathrm{0.090X}_{\mathrm{Cu}}\mathrm{+0.892X}_{\mathrm{Ga}}\mathrm{+0.210X}_{\mathrm{As}}\mathrm{+0.009X}_{\mathrm{Rb}}- \\ & \quad\quad\; \; \mathrm{1.796X}_{\mathrm{Sr}}-\mathrm{2.461X}_{\mathrm{Cd}}\mathrm{-0.012X}_{\mathrm{Ba}}\mathrm{+0.813X}_{\mathrm{Tl}}- \\ & \quad\quad\; \; \mathrm{0.046X}_{\delta^2\mathrm{H}}\mathrm{+0.367X}_{\delta^{18}\mathrm{O}}-\mathrm{0.288X}_{\delta^{34}\mathrm{S}}\mathrm{+0.175X}_{\mathrm{Cs}}\end{split} $
$ \begin{split} & \mathrm{Y3=-8.676+1.394X}_{\mathrm{Al}}\mathrm{+0.858X}_{\mathrm{Mn}}\mathrm{-0.012X}_{\mathrm{Fe}}- \\ & \quad\quad\; \; \mathrm{0.040X}_{\mathrm{Cu}}\mathrm{+0.076X}_{\mathrm{Ga}}\mathrm{+52.717X}_{\mathrm{As}}\mathrm{-0.015X}_{\mathrm{Rb}}- \\ & \quad\quad\; \; \mathrm{23.729X}_{\mathrm{Sr}}\mathrm{+10.008X}_{\mathrm{Cd}}\mathrm{+0.020X}_{\mathrm{Ba}}\mathrm{-9.462X}_{\mathrm{Tl}}- \\ & \quad\quad\; \; \mathrm{0.060X}_{\delta^2\mathrm{H}}+\mathrm{0.041X}_{\delta^{18}\mathrm{O}\mathrm{ }}\mathrm{+0.619X}_{\mathit{\delta}\mathrm{^{34}S}}\mathrm{+0.725X}_{\mathrm{Cs}}\end{split} $
特征值分析表明,第一判别函数的方差贡献率为83.1%,第二判别函数的方差贡献率为9.1%,第三判别函数的方差贡献率为7.9%,三个函数累积方差贡献率为100%。以第一判别函数和第二判别函数为横纵坐标,根据组质心函数(表7)绘制散点图(图4)。由图4可知,不同产地的大叶种晒青茶分离效果较好,景洪市和思茅区可以完全区分开,宁洱县和梁河县组质心距离较近,出现轻微重叠现象,与OPLS-DA结果一致。为验证模型的有效性,利用判别函数对80个样品进行判别分类,并结合“留一法”对模型进行回代检验和交叉验证。结果如表8所示,模型正确地对100.0%个原始已分组茶叶样品进行了分类,且交叉验证率大于80%,其中10%宁洱县的茶叶被误判在了梁河县,20%梁河县的茶叶被误判在了宁洱县。同样的,刘宏程等[40]基于不同茶叶元素含量差异,建立了普洱茶的产地判别模型,其线性判别分析的回判与验证成功率均达到100%。相比之下,本实验判别率相对较低,可能是部分样本来源地缘相近,导致土壤矿质元素组成相似,从而影响模型对产地的区分能力。
茶叶生长环境的气候、水质、土壤性质、微生物种群及加工方式等不同会导致不同产地茶叶中微量元素、稀土元素和稳定同位素的种类和含量差异。本实验用电感耦合等离子体串联质谱(ICP-MS/MS)测定了宁洱县、梁河县、思茅区、景洪市等80个茶叶样品中的43种元素,利用SPSS进行主成分和判别分析。实验发现4个产地茶叶中元素总量梁河县显著高于其他三地(P<0.05)最高,宁洱县次之,其余两地较少。利用PCA提取7个主成分的累计方差贡献率达到80.831%,且筛选出VIP值>1的15个特征差异指标(δ2H、δ18O、Rb、Al、Tl、Cs、δ34S、Mn、Cu、Cd、Ga、Ba、Fe、As、Sr)用于Fisher线性判别分析,建立了3个典型判别函数,通过回代检验,完全可以实现对抽取的不同产地的茶叶进行100%正确判别,且交叉验证正确率大于80%,不仅如此,SVM的分类正确率为93.75%,KNN的分类正确率为100%。研究表明,不同产地的多元素含量可为云南大叶种晒青茶的产地溯源提供一个新方法,为云南大叶种晒青茶的原产地保护提供参考和借鉴。

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2026年第47卷第17期
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doi: 10.13386/j.issn1002-0306.2025080105
  • 接收时间:2025-08-11
  • 首发时间:2026-10-24
  • 出版时间:2026-09-01
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  • 收稿日期:2025-08-11
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    1云南省农业科学院质量标准与检测技术研究所,云南昆明 650205
    2云南农业大学食品科学技术学院,云南昆明 650201

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刘兴勇(1985−),男,硕士,助理研究员,研究方向:农产品质量安全,E-mail:。
邵金良(1979−),男,硕士,研究员,研究方向:农产品质量安全与品质评价,E-mail:。
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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