Article(id=1217779720746353425, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217779717386715826, articleNumber=null, orderNo=null, doi=10.19812/j.cnki.jfsq11-5956/ts.20241231001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1735574400000, receivedDateStr=2024-12-31, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1768270910678, onlineDateStr=2026-01-13, pubDate=1750780800000, pubDateStr=2025-06-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1768270910678, onlineIssueDateStr=2026-01-13, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1768270910678, creator=13701087609, updateTime=1768270910678, updator=13701087609, issue=Issue{id=1217779717386715826, tenantId=1146029695717560320, journalId=1149652044408987649, year='2025', volume='16', issue='12', pageStart='1', pageEnd='320', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1768270909877, creator=13701087609, updateTime=1768299620707, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1217900139386163208, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217779717386715826, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1217900139386163209, tenantId=1146029695717560320, journalId=1149652044408987649, issueId=1217779717386715826, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=40, endPage=49, ext={EN=ArticleExt(id=1217779721094480680, articleId=1217779720746353425, tenantId=1146029695717560320, journalId=1149652044408987649, language=EN, title=Identification of Fuping goat milk by multi-element analysis combined with chemometrics, columnId=1217779718456263351, journalTitle=Journal of Food Safety & Quality, columnName=Highlight: “The 14th Five-Year Plan” National Key Research and Development Program of China—Key Technology Research and Standardized Application for Panoramic Analysis of Food Authenticity, runingTitle=null, highlight=null, articleAbstract=

Objective To achieve the geographical discrimination of Fuping goat milk using microwave digestion combined with inductively coupled plasma mass spectrometry (ICP-MS) and chemometric methods. Methods A total of 70 goat milk samples were collected from 7 regions in Shaanxi Province, including Baoji, Hanzhong, Jingyang County and Qian County (both in Xianyang), Weinan, Xi’an and Yan’an. They were lyophilized to milk powder, and after microwave digestion, the digested solution was analyzed using ICP-MS. Principal component analysis (PCA) and orthogonal partial least squares-discrimination analysis (OPLS-DA) were employed to discriminate goat milk from different origins. Results A total of 42 kinds of elements in the milk powder from 7 different origins were detected. The concentrations of K, Ca, Fe, Zn, Si and Na were relatively high, followed by B, Ti, Mg, Al, Cu and Ba, while other elements were found in lower concentrations, particularly the rare earth elements such as Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Lu, Ho and Y, which were present in negligible amounts. The 7 origins were divided into two groups based on distance: Group I (Baoji; Hanzhong; Weinan; Yan’an) and Group II (Jingyang County, Qian County of Xianyang; Weinan; Xi’an). OPLS-DA model was applied to both groups, with accuracy rates of 95.12% and 87.80%, respectively. Among them, the accuracy of samples from Fuping County-Weinan City was 100%. In Group I, the content differences of Ba, Mn, Si, Zn, Se, Na and B were the primary factors for origin discrimination. While in Group II, Se, B and Ni elements contributed significantly to the origin discrimination. Geographical distance was the most important factor to distinguish goat milk from different origins. While the data of 6 goat milk samples from Fuping County-Weinan City were imported into both Group I and Group II models for validation, the discrimination accuracy was 100% for both groups. Conclusion The established multi-element analysis combined with chemometrics could achieve rapid and accurate identification of Fuping goat milk from small-scale regions (>50 km).

, correspAuthors=Zi-Juan ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, 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, authorCompany=null, fund=null, authors=null, authorsList=Jia-Lin ZHANG, Qiao-Ying CHANG, Yong-Xiang ZHU, Zi-Juan ZHANG), CN=ArticleExt(id=1217779722340189051, articleId=1217779720746353425, tenantId=1146029695717560320, journalId=1149652044408987649, language=CN, title=多元素分析结合化学计量学方法鉴别富平山羊乳, columnId=1217779718691144379, journalTitle=食品安全质量检测学报, columnName=本期重点:“十四五”国家重点研发计划——食品真实性全景分析关键技术研究与标准化应用, runingTitle=null, highlight=null, articleAbstract=

目的 采用微波消解与电感耦合等离子体质谱(inductively coupled plasma-mass spectrometry, ICP-MS)法结合化学计量学方法实现富平山羊乳的产地鉴别。方法 从陕西省内的宝鸡市、汉中市、咸阳市泾阳县、咸阳市乾县、渭南市、西安市、延安市7个地区共采集70个羊乳样品, 冻干成乳粉, 经消解后, 采用ICP-MS对消解液进行检测, 通过主成分分析(principal component analysis, PCA)与正交偏最小二乘判别分析(orthogonal partial least squares-discrimination analysis, OPLS-DA)对不同产地羊乳进行区分。结果 对7个产地的羊乳粉中42种元素进行检测, K、Ca、Fe、Zn、Si、Na的含量较高, 其次是B、Ti、Mg、Al、Cu、Ba, 其他元素含量相对较低, 尤其是Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Lu、Ho、Y等稀土元素含量甚微。按距离将7个产地分为I(宝鸡市、汉中市、渭南市、延安市)、II(咸阳市泾阳县、咸阳市乾县、渭南市、西安市)两组, 分别采用OPLS-DA模型分析, 准确率分别为95.12%、87.80%, 其中渭南市富平县判别准确率均为100%。对于组I, Ba、Mn、Si、Zn、Se、Na、B元素含量差异为产地区分的主要因素, 对于组II, Se、B、Ni元素对产地区分贡献较大。地理距离是影响羊乳产地鉴别的重要因素。将6个渭南市富平县羊乳样品数据分别导入组I、组II模型进行验证, 判别准确率均为100%。结论 本研究建立的多元素分析结合化学计量学方法可实现小尺度(50 km以上)范围内富平山羊乳的快速、准确识别。

, correspAuthors=张紫娟, authorNote=null, correspAuthorsNote=
*张紫娟(1974—), 女, 博士, 副研究员, 主要研究方向为食品安全和食品真实性检测。E-mail:
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张佳琳(1997—), 女, 助理实验员, 主要研究方向为食品安全和食品真实性检测。E-mail:

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张佳琳(1997—), 女, 助理实验员, 主要研究方向为食品安全和食品真实性检测。E-mail:

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Food Chemistry, 2020, 316: 126332., articleTitle=A case of milk traceability in small-scale districts-Inner Mongolia of China by nutritional and geographical parameters, refAbstract=null)], funds=[Fund(id=1217833934285623819, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, awardId=2023YFF1104702, language=CN, fundingSource=国家重点研发计划项目(2023YFF1104702), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1217833927230804031, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, xref=1, ext=[AuthorCompanyExt(id=1217833927234998336, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, companyId=1217833927230804031, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 Agro-product Safety Research Center, Chinese Academy of Quality and Inspection & Testing, Beijing 100176, China), AuthorCompanyExt(id=1217833927247581249, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, companyId=1217833927230804031, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 中国质量检验检测科学研究院农产品安全研究中心, 北京 100176)]), AuthorCompany(id=1217833927352438862, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, xref=2, ext=[AuthorCompanyExt(id=1217833927360827472, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, companyId=1217833927352438862, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 Key Laboratory of Food Authenticity Identification, State Administration for Market Regulation, Beijing 100176, China), AuthorCompanyExt(id=1217833927373410386, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, companyId=1217833927352438862, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 国家市场监督管理总局重点实验室(食品真实性鉴别), 北京 100176)])], figs=[ArticleFig(id=1217833932289134979, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=EN, label=Fig.1, caption=Collection locations of goat milk samples, figureFileSmall=lWtIjZJ1C///npOGp7bBDg==, figureFileBig=rNMUBo5+/WO0GWrIV2MZ8A==, tableContent=null), ArticleFig(id=1217833932444324237, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=CN, label=图1, caption=羊乳样品采集地点图, figureFileSmall=lWtIjZJ1C///npOGp7bBDg==, figureFileBig=rNMUBo5+/WO0GWrIV2MZ8A==, tableContent=null), ArticleFig(id=1217833932616290711, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=EN, label=Fig.2, caption=Score (A) and loading (B) plots of goat milk from 7 origins in PCA model, figureFileSmall=Sn7pJWInwSGIbvZRO1vaSA==, figureFileBig=shSLccykDMRCEew93pGyMw==, tableContent=null), ArticleFig(id=1217833932771479969, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=CN, label=图2, caption=PCA模型对7个产地山羊乳区分的得分图(A)和载荷图(B), figureFileSmall=Sn7pJWInwSGIbvZRO1vaSA==, figureFileBig=shSLccykDMRCEew93pGyMw==, tableContent=null), ArticleFig(id=1217833932897309098, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=EN, label=Fig.3, caption=Score (A, a), VIP (B, b) and loading (C, c) plots of goat milk from 7 origins in OPLS-DA model, figureFileSmall=4ELLSxg/3Q0NiCQY54v9mg==, figureFileBig=Bh57wB+0eJpgtoraV922Cg==, tableContent=null), ArticleFig(id=1217833933023138224, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=CN, label=图3, caption=OPLS-DA模型对7个产地山羊乳区分的得分图(A、a)VIP图(B、b)和载荷图(C、c)

注: A、B、C代表42种元素分析结果; a、b、c代表26种元素分析结果; VIP图中红色代表VIP值大于1, 绿色代表VIP值小于1; B中1~42分别为Se82、Ti48、B11、Ba138、Mn55、Zn66、Cd111、Si28、Na23、Cu63、Ag107、K39、Pb208、Mo98、Be9、Ca43、Sc45、Lu175、Al27、Pr141、Eu153、Sm152、Nd142、Fe57、As75、Cr52、Co59、Tm169、Mg24、La139、Er166、Dy164、Y89、Tl205、Ho165、Sb121、Gd158、Tb159、Yb174、Ce140、Ni60、V51。

, figureFileSmall=4ELLSxg/3Q0NiCQY54v9mg==, figureFileBig=Bh57wB+0eJpgtoraV922Cg==, tableContent=null), ArticleFig(id=1217833933169938875, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=EN, label=Fig.4, caption=2D score (A, a), 3D score (B, b), VIP (C, c) and loading (D, d) plots of group I goat milk in OPLS-DA model, figureFileSmall=w4YnCd1ZHpPb7thHk0yuBQ==, figureFileBig=EBY/RCri3ts8znvSU3hZyw==, tableContent=null), ArticleFig(id=1217833933253824962, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=CN, label=图4, caption=OPLS-DA模型对组I羊乳区分的2D得分图(A、a)、3D得分图(B、b)、VIP图(C、c)和载荷图(D、d)

注: A、B、C、D代表42种元素分析结果; a、b、c、d代表26种元素分析结果; VIP图中红色代表VIP值大于1, 绿色代表VIP值小于1; 图5同。C中1~42分别为Ba138、Mn55、Si28、Zn66、Se82、Na23、B11、Cd111、Cu63、Ag107、K39、Mo98、Y89、Yb174、Be9、Pb208、Al27、Nd142、Dy164、Sc45、Pr141、Sm152、Er166、Lu175、La139、Ca43、Eu153、Sb121、Co59、Tl205、Gd158、Fe57、Tm169、Mg24、Cr52、Ho165、Tb159、Ce140、As75、Ni60、Ti48、V51。

, figureFileSmall=w4YnCd1ZHpPb7thHk0yuBQ==, figureFileBig=EBY/RCri3ts8znvSU3hZyw==, tableContent=null), ArticleFig(id=1217833933367071178, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=EN, label=Fig.5, caption=2D score (A, a), 3D score (B, b), VIP (C, c) and loading (D, d) plots of group II goat milk in OPLS-DA model, figureFileSmall=ElW6GA9O+e4OLu8IR1n2pw==, figureFileBig=oDQBM16DkXtaJH9SG/dLFA==, tableContent=null), ArticleFig(id=1217833933497094609, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=CN, label=图5, caption=OPLS-DA模型对组II羊乳区分的2D得分图(A、a)、3D得分图(B、b)、VIP图(C、c)和载荷图(D、d)

注: C中1~42分别为Se82、B11、Ni60、Mn55、Ti48、Cd111、Mo98、Cu63、Si28、Pb208、Ag107、Be9、K39、Sc45、Nd142、Mg24、Ca43、Al27、Cr52、Eu153、Pr141、As75、Sm152、Zn66、Co59、Er166、Tm169、Lu175、Tb159、Ho165、La139、Gd158、Dy164、Fe57、Ce140、Y89、Sb121、Ba138、V51、Na23、Yb174、Tl205。

, figureFileSmall=ElW6GA9O+e4OLu8IR1n2pw==, figureFileBig=oDQBM16DkXtaJH9SG/dLFA==, tableContent=null), ArticleFig(id=1217833933585175004, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=EN, label=Fig.6, caption=Prediction results of goat milk samples, figureFileSmall=+DMEY/kTWRHr1n3GzjEXOA==, figureFileBig=orXi1VFh8kHDqtZ8qSO9+g==, tableContent=null), ArticleFig(id=1217833933673255398, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=CN, label=图6, caption=羊乳样品预测结果

注: 灰色(Default)代表预测样品; A. 组I OPLS-DA模型3D得分图; B. 组II OPLS-DA模型3D得分图。

, figureFileSmall=+DMEY/kTWRHr1n3GzjEXOA==, figureFileBig=orXi1VFh8kHDqtZ8qSO9+g==, tableContent=null), ArticleFig(id=1217833933786501614, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=EN, label=Table 1, caption=

R2X, R2Y and Q2 for different OPLS-DA models

, figureFileSmall=null, figureFileBig=null, tableContent=
分类 所有样品 组I 组II
42 26 42 26 42 26
R2X 0.682 0.555 0.642 0.384 0.422 0.381
R2Y 0.49 0.441 0.725 0.646 0.518 0.567
Q2 0.22 0.253 0.431 0.44 0.273 0.361
), ArticleFig(id=1217833933954273784, tenantId=1146029695717560320, journalId=1149652044408987649, articleId=1217779720746353425, language=CN, label=表1, caption=

各OPLS-DA模型的R2X、R2Y及Q2

, figureFileSmall=null, figureFileBig=null, tableContent=
分类 所有样品 组I 组II
42 26 42 26 42 26
R2X 0.682 0.555 0.642 0.384 0.422 0.381
R2Y 0.49 0.441 0.725 0.646 0.518 0.567
Q2 0.22 0.253 0.431 0.44 0.273 0.361
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多元素分析结合化学计量学方法鉴别富平山羊乳
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张佳琳 1, 2 , 常巧英 1, 2 , 祝永祥 1 , 张紫娟 1, 2, *
食品安全质量检测学报 | 本期重点:“十四五”国家重点研发计划——食品真实性全景分析关键技术研究与标准化应用 2025,16(12): 40-49
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食品安全质量检测学报 | 本期重点:“十四五”国家重点研发计划——食品真实性全景分析关键技术研究与标准化应用 2025, 16(12): 40-49
多元素分析结合化学计量学方法鉴别富平山羊乳
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张佳琳1, 2 , 常巧英1, 2, 祝永祥1, 张紫娟1, 2, *
作者信息
  • 1 中国质量检验检测科学研究院农产品安全研究中心, 北京 100176
  • 2 国家市场监督管理总局重点实验室(食品真实性鉴别), 北京 100176
  • 张佳琳(1997—), 女, 助理实验员, 主要研究方向为食品安全和食品真实性检测。E-mail:

通讯作者:

*张紫娟(1974—), 女, 博士, 副研究员, 主要研究方向为食品安全和食品真实性检测。E-mail:
Identification of Fuping goat milk by multi-element analysis combined with chemometrics
Jia-Lin ZHANG1, 2 , Qiao-Ying CHANG1, 2, Yong-Xiang ZHU1, Zi-Juan ZHANG1, 2, *
Affiliations
  • 1 Agro-product Safety Research Center, Chinese Academy of Quality and Inspection & Testing, Beijing 100176, China
  • 2 Key Laboratory of Food Authenticity Identification, State Administration for Market Regulation, Beijing 100176, China
出版时间: 2025-06-25 doi: 10.19812/j.cnki.jfsq11-5956/ts.20241231001
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目的 采用微波消解与电感耦合等离子体质谱(inductively coupled plasma-mass spectrometry, ICP-MS)法结合化学计量学方法实现富平山羊乳的产地鉴别。方法 从陕西省内的宝鸡市、汉中市、咸阳市泾阳县、咸阳市乾县、渭南市、西安市、延安市7个地区共采集70个羊乳样品, 冻干成乳粉, 经消解后, 采用ICP-MS对消解液进行检测, 通过主成分分析(principal component analysis, PCA)与正交偏最小二乘判别分析(orthogonal partial least squares-discrimination analysis, OPLS-DA)对不同产地羊乳进行区分。结果 对7个产地的羊乳粉中42种元素进行检测, K、Ca、Fe、Zn、Si、Na的含量较高, 其次是B、Ti、Mg、Al、Cu、Ba, 其他元素含量相对较低, 尤其是Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Lu、Ho、Y等稀土元素含量甚微。按距离将7个产地分为I(宝鸡市、汉中市、渭南市、延安市)、II(咸阳市泾阳县、咸阳市乾县、渭南市、西安市)两组, 分别采用OPLS-DA模型分析, 准确率分别为95.12%、87.80%, 其中渭南市富平县判别准确率均为100%。对于组I, Ba、Mn、Si、Zn、Se、Na、B元素含量差异为产地区分的主要因素, 对于组II, Se、B、Ni元素对产地区分贡献较大。地理距离是影响羊乳产地鉴别的重要因素。将6个渭南市富平县羊乳样品数据分别导入组I、组II模型进行验证, 判别准确率均为100%。结论 本研究建立的多元素分析结合化学计量学方法可实现小尺度(50 km以上)范围内富平山羊乳的快速、准确识别。

山羊乳  /  多元素分析  /  化学计量学  /  正交偏最小二乘判别分析法  /  电感耦合等离子体质谱法  /  产地鉴别

Objective To achieve the geographical discrimination of Fuping goat milk using microwave digestion combined with inductively coupled plasma mass spectrometry (ICP-MS) and chemometric methods. Methods A total of 70 goat milk samples were collected from 7 regions in Shaanxi Province, including Baoji, Hanzhong, Jingyang County and Qian County (both in Xianyang), Weinan, Xi’an and Yan’an. They were lyophilized to milk powder, and after microwave digestion, the digested solution was analyzed using ICP-MS. Principal component analysis (PCA) and orthogonal partial least squares-discrimination analysis (OPLS-DA) were employed to discriminate goat milk from different origins. Results A total of 42 kinds of elements in the milk powder from 7 different origins were detected. The concentrations of K, Ca, Fe, Zn, Si and Na were relatively high, followed by B, Ti, Mg, Al, Cu and Ba, while other elements were found in lower concentrations, particularly the rare earth elements such as Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er, Tm, Yb, Lu, Ho and Y, which were present in negligible amounts. The 7 origins were divided into two groups based on distance: Group I (Baoji; Hanzhong; Weinan; Yan’an) and Group II (Jingyang County, Qian County of Xianyang; Weinan; Xi’an). OPLS-DA model was applied to both groups, with accuracy rates of 95.12% and 87.80%, respectively. Among them, the accuracy of samples from Fuping County-Weinan City was 100%. In Group I, the content differences of Ba, Mn, Si, Zn, Se, Na and B were the primary factors for origin discrimination. While in Group II, Se, B and Ni elements contributed significantly to the origin discrimination. Geographical distance was the most important factor to distinguish goat milk from different origins. While the data of 6 goat milk samples from Fuping County-Weinan City were imported into both Group I and Group II models for validation, the discrimination accuracy was 100% for both groups. Conclusion The established multi-element analysis combined with chemometrics could achieve rapid and accurate identification of Fuping goat milk from small-scale regions (>50 km).

goat milk  /  multiple elements analysis  /  chemometrics  /  orthogonal partial least squares discriminant analysis  /  inductively coupled plasma-mass spectrometry  /  geographical origin identification
张佳琳, 常巧英, 祝永祥, 张紫娟. 多元素分析结合化学计量学方法鉴别富平山羊乳. 食品安全质量检测学报, 2025 , 16 (12) : 40 -49 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20241231001
Jia-Lin ZHANG, Qiao-Ying CHANG, Yong-Xiang ZHU, Zi-Juan ZHANG. Identification of Fuping goat milk by multi-element analysis combined with chemometrics[J]. Journal of Food Safety & Quality, 2025 , 16 (12) : 40 -49 . DOI: 10.19812/j.cnki.jfsq11-5956/ts.20241231001
羊乳具有“补寒冷虚, 润心肺, 治消渴; 疗虚劳, 益精气, 补肺、肾气和小肠气”等功效, 是世界上第三大乳源[1]。《本草纲目》《食疗本草》《千金方》等典籍均有对羊乳的介绍[2]。山羊乳营养成分更接近于人乳[3], 其有望作为乳寡糖的替代来源, 应用于婴儿配方奶粉中[4]。我国的羊乳产地主要集中在陕西、山东、云南和河南等地, 其中陕西省的羊乳产业规模和影响力最大, 被誉为世界三大羊奶产地之一。陕西省渭南市富平县位于关中平原地区, 气候温和, 优越的地理条件和气候条件适宜奶山羊的饲养, 产出的羊乳品质佳, 价值高[5], 富平羊乳粉已成为地理标志产品[6]。不同产地山羊乳因地域、环境等的差异, 其元素组成及含量有所不同。不法商家为牟取利益, 虚假宣传、谎报产地, 严重侵犯了消费者的合法权益, 也对富平羊乳的声誉产生一定影响。
元素分析常用的技术有电感耦合等离子体质谱法(inductively coupled plasma-mass spectrometry, ICP-MS)、电感耦合等离子体发射光谱法、有机元素分析法等, 其中ICP-MS具有灵敏度高、选择性高的优点, 且可以实现多种元素同时分析, 近年来, 随着分析技术的发展, 微波消解结合ICP-MS已成为一种有效的样品前处理和元素分析手段, 广泛应用于食品[7-10]、环境[11-14]、生物样品[15-17]等领域。该技术快速、高效、灵敏度高, 能够准确测定样品中的微量元素和痕量元素[18]。由于地貌不同、气候不同, 各地区具有独特的元素组成, 地理因素的差别导致在不同地区养殖、种植的动植物体内多种元素含量有所区别, 因此,多元素分析技术成为农食产品产地鉴别的主要手段之一。目前, ICP-MS技术在乳品方面的研究主要集中在无机元素含量的检测[19-21], 化学计量学方法的应用, 如主成分分析(principal component analysis, PCA)、正交偏最小二乘判别分析(orthogonal partial least squares discrimination analysis, OPLS-DA)、随机森林(random forest, RF)、支持向量机(support vector machine, SVM)等, 为复杂数据的解析提供了强有力的工具, 使基于元素指纹的产地鉴别成为可能, 并得到了较好的应用[22-27]。但在乳品方面, 化学计量学结合元素分析仍大多用于不同类型乳间鉴别等[28-30], 而对小地域范围内同种类型乳的鉴别非常少见。
本研究旨在建立一种微波消解结合ICP-MS和化学计量学方法的鉴别模型, 以实现山羊乳在小尺度地域范围内, 特别是富平羊乳的准确鉴别。通过分析不同产地羊乳中的元素组成及含量, 结合化学计量学方法进行分析, 揭示不同产地山羊乳中元素特征的差异, 为富平山羊乳的地域鉴别提供科学依据。
70个羊乳样品于2024年5月在陕西省宝鸡市(B)、汉中市(H)、咸阳市泾阳县(J)、咸阳市乾县(Q)、渭南市(W)、西安市(X)、延安市(Y) 7个地区采集(地理位置见图1), 各产地10个样品。样品采集后立即冷冻, 冷链运输, 分装后-18 ℃保存。
硝酸(HNO3)(电子级G3, 国药集团化学试剂有限公司); 多元素标准溶液[银(Ag)、铝(Al)、砷(As)、硼(B)、钡(Ba)、铍(Be)、钙(Ca)、镉(Cd)、钴(Co)、铬(Cr)、铜(Cu)、铁(Fe)、镁(Mg)、锰(Mn)、钼(Mo)、钠(Na)、镍(Ni)、铅(Pb)、锑(Sb)、硒(Se)、钛(Ti)、铊(Tl)、钒(V)、锌(Zn)质量浓度为100 μg/mL, 钾(K)质量浓度为1000 μg/mL, 硅(Si)质量浓度为50 μg/mL, 加拿大SCP Science公司]; 稀土元素+钪元素混合标准溶液[钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钪(Sc)质量浓度为100 μg/mL]、铑标准溶液(Rh, 质量浓度1000 μg/mL)(中国钢研纳克检测技术股份有限公司); 乳粉标准物质(GBW10115、GBW10116, 国家标准物质资源共享平台)。
NexlON 350X电感耦合等离子体质谱仪(美国PerkinElmer公司); UltraWAVE ECR微波消解系统(意大利Milestone公司); BS210S型电子天平(精度0.1 mg, 德国Sartorius公司); Milli-Q超纯水系统(美国Millipore公司); Cell 4-1真空冷冻干燥系统(北京立德泰科技有限公司); AI-206型温度控制器(厦门宇电自动化科技有限公司)。
多元素标准溶液与稀土元素混合标准溶液分别用1% HNO3 (V:V, 下同)逐级稀释, 配制质量浓度为0.1、0.2、0.5、1.0、2.0、10.0、40.0、200.0 ng/mL的标准曲线用工作溶液。
Rh标准溶液用1% (V:V) HNO3稀释至1 ng/mL, 作为内标溶液。
冷冻的羊乳样品于真空冷冻干燥机中冻干成乳粉, 4 ℃密封保存。精确称取50.0 mg乳粉于消解管中, 加入2 mL HNO3, 置于微波消解系统内, 密闭加压40 bar, 按下列程序进行消解: 初始, 室温; 10 min, 220 ℃; 20 min, 240 ℃, 保持15 min; 35 min, 开始降温。消解完全后, 将消解管置于温控器上150 ℃赶酸约1 h, 至消解液剩余约200 μL。冷却至室温后, 用适量纯水洗涤消解管3次, 合并液体并定容至10 mL, 摇匀。对照样品按相同方法制备, 空白样品除不加乳粉外按相同方法制备。
ICP射频功率1600 W, 石英旋流喷雾室, 同心石英雾化器, 雾化器气体流量0.95 L/min, 辅助气流量1.2 L/min, 等离子体气流量18 L/min, 质量过滤器为四极杆, 检测器为脉冲/模拟双检测器, 数据采集重复3次, 采用自动进样器, 进样时间75 s。
内标溶液经蠕动泵实时进样。样品溶液中元素测定值超出标准曲线范围后, 需用1% HNO3稀释至线性范围内, 再重新测定。检测时每两个产地的样品间插入一个空白溶液以避免对结果产生干扰。
仪器根据建立的标准曲线自动计算出各待测元素的质量浓度, 将其代入下列公式(1)计算出羊乳粉中各元素含量。
Ci=$\frac{(\rho -{\rho }_{0})\times V\times f}{m\times 1000}$
式中: Ci为样品中i元素的含量, mg/kg; ρ为样品中待测元素质量浓度, ng/mL; ρ0为空白对照中待测元素质量浓度, ng/mL; V为样品消化液定容体积, mL; f为稀释倍数; m为样品质量, g; 1000为换算系数。
将整理好的样品数据导入SIMCA软件采用PCA和OPLS-DA模型进行分析。
将陕西省宝鸡市、汉中市、咸阳市泾阳县、咸阳市乾县、渭南市、西安市、延安市7个地区的羊乳粉元素含量进行汇总, 羊乳粉中各元素含量存在差异。总体来看, K、Ca、Fe、Zn、Si、Na的含量较高, 均大于10 mg/kg, 其次是B、Ti、Mg、Al、Cu、Ba, 含量在1~10 mg/kg之间, 其他元素含量相对较低, 尤其是Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Lu、Ho、Y等稀土元素含量甚微。渭南市Fe、Co、Pb平均含量均较高, 而As元素含量最大值为0.018 mg/kg, 低于其他6个地区的最大值。
将计算出的所有羊乳的元素含量数据进行PCA分析, 得分图如图2所示, 可以发现只有汉中市样品得到有效区分, 渭南市和宝鸡市的样品相对其他地区样品较为集中, 而地图中显示7个地区中只有汉中市地理位置相对偏西南方向, 因此可能由于地理位置不同, 导致水源、饲草等元素含量存在差异, 进而影响羊乳中元素含量。
采用OPLS-DA模型分析7个产地羊乳42个元素, R2XR2YQ2表1, 得分图见图3A, 与PCA模型基本一样, 只能将汉中市样品区分开来。图3B为变量投影重要性分析值(variable importance in projection, VIP)图, 红色代表VIP值大于1的变量, 共13个, 分别为Se、Ti、B、Ba、Mn、Zn、Cd、Si、Na、Cu、Ag、K、Pb, 其中Se、Ti的VIP值大于1.5, 说明二者对此模型的贡献能力相对更大, 根据元素含量的平均值, 发现汉中市样品与其他6个地区相比Se和Ti含量均最低, 这可能是得以区分的原因之一。图3C为载荷图, 结果显示Si、B、Ba、Na、Mn、Zn、Se、Ti等对产地区分作出的贡献较大。
进一步降低数据维度, 删除羊乳中不含或含量极低的Ag、Be、Cd、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Lu、Ho、Y共16个元素, 对剩余的26个元素同样采用OPLS-DA模型分析, R2XR2YQ2表1, 与降维前结果相差不大, 图3a为得分图, 发现依然只能将汉中市样品单独区分开。图3b的VIP图中显示, VIP值大于1的变量有9个, 分别为B、Se、Ti、Ba、Si、Mn、Zn、Na、Sc, 与图3c的载荷图结果基本一致。与数据降维前相比, 对羊乳产地区分结果无有效改善。
样品按照相距渭南市富平县的距离, 将7个地区羊乳按距离分为组I (150~300 km, 宝鸡市、汉中市、渭南市、延安市)和组II (40~100 km, 咸阳市泾阳县、咸阳市乾县、渭南市、西安市)两组, 分别采用OPLS-DA模型分析。
将组I中4个产地(宝鸡市、汉中市、渭南市、延安市)所有42个羊乳元素数据采用OPLS-DA模型分析, R2XR2YQ2表1, 2D和3D得分图分别见图4A图4B, 发现2D图可将汉中市和延安市样品明显区分, 渭南市与宝鸡市样品有部分交叉, 而3D图区分效果好, 结果更直观。图4C为VIP图, 有11个变量VIP值大于1, 按VIP值从大到小分别为Ba、Mn、Si、Zn、Se、Na、B、Cd、Cu、Ag、K, 其中Ba、Mn、Si、Zn、Se的VIP值大于1.5, 而载荷图(图4D)中显示Ba、Si、B、Na、Mn、Zn、Se对产地区分贡献较大, 这与VIP值大于1中前7个变量一致, 说明Ba、Mn、Si、Zn、Se、Na、B这7种元素对宝鸡市、汉中市、渭南市、延安市这4个产地的羊乳区分做出了重要贡献。渭南市与宝鸡市样品的Ba元素平均含量相近, 分别为0.793 mg/kg和0.759 mg/kg, 可能由此导致2D得分图中两地存在交叉现象, 汉中市与延安市样品的Ba、Mn、Se、B元素平均含量相差较大, 因此两地区分较明显, 而Si元素在4个产地中的平均含量相差较大, 由高到低分别为汉中市60.780 mg/kg、宝鸡市40.430 mg/kg、渭南市33.765 mg/kg、延安市18.340 mg/kg, 这可能是4个产地得以区分的主要因素。此模型的判别准确率为95.12%, 其中渭南市的准确率为100%, 在相对较远距离的模型中渭南市富平县羊乳判别准确率高。
将降维后的26个羊乳元素数据采用OPLS-DA模型分析, R2XR2YQ2表1所示, 图4a图4b分别为2D和3D得分图, 结果与46个元素时基本一致。VIP图(图4c)显示VIP值大于1的变量有10个, 从大到小分别为Ba、B、Si、Mn、Zn、Se、Na、K、Cu、Sc, 其中Ba元素的VIP值大于1.5, 此外4个产地羊乳中K (66.335~72.635 mg/kg)、Cu (1.101~1.476 mg/kg)元素平均含量基本一致, 而Sc含量均较低(<0.100 mg/kg), 因此3种元素虽VIP值略大于1, 但对产地区分贡献较小。载荷图(图4d)显示Ba、Si、B、Na、Mn、Zn、Se对产地区分贡献较大, 与VIP值大于1的变量一致(K、Cu、Sc除外), 因此, 影响宝鸡市、汉中市、渭南市、延安市羊乳产地区分的主要因素为Ba、Mn、Si、Zn、Se、Na、B这7种元素, 此模型的判别准确率为95.12%, 其中渭南市的准确率为100%, 与降低维度前结果一致。
将组II中4个产地(咸阳市泾阳县、咸阳市乾县、渭南市、西安市)所有42个羊乳元素数据采用OPLS-DA模型分析, R2XR2YQ2结果见表1, 2D和3D得分图分别见图5A图5B, 发现渭南市样品可相对较好的被区分开, 且渭南市与咸阳市泾阳县样品区分更加明显。图5C为VIP图, 有12个变量VIP值大于1, 按VIP值从大到小分别为Se、B、Ni、Mn、Ti、Cd、Mo、Cu、Si、Pb、Ag、Be, 其中Se和B元素的VIP值大于2, Ni元素的VIP值大于1.5, 说明Se、B、Ni对模型贡献较大。渭南市样品Se元素平均含量最低(0.173 mg/kg)、B元素平均含量最高(6.942 mg/kg), 咸阳市泾阳县样品Se元素平均含量最高(0.258 mg/kg)、B元素平均含量最低(5.566 mg/kg), 故两地区分明显, 此外, 对于Ni元素, 渭南市样品平均含量最高, 为0.499 mg/kg, 而咸阳市泾阳县、咸阳市乾县、西安市平均含量水平相当, 为0.313~0.364 mg/kg, 故渭南市样品可完全区分。载荷图(图5D)中显示对产地区分贡献较大的元素除与VIP值大于1的元素基本一致, 还有Sm、Pr、Eu、Tb、Ho、Tm、Nd、Lu、Dy、Er等稀土元素及Sc元素含量非常低(<0.100 mg/kg), 因此认为对产地区分贡献不大。此模型的判别准确率为87.80%, 但对于渭南市来说准确率为100%, 说明此模型对渭南市富平县羊乳判别准确率较高。
将降维后的26个羊乳元素数据采用OPLS-DA模型分析, R2XR2YQ2表1, 图5a图5b分别为2D和3D得分图, 结果与46个元素时基本一致。VIP图(图5c)显示VIP值大于1的变量有8个, 从大到小分别为Se、B、Ni、Ti、Mn、Si、Mo、Cu, 其中Se、B、Ni元素的VIP值大于1.5, 说明其对模型贡献相对更大。载荷图(图5d)中距离原点较远的变量除与VIP值大于1一致的变量外, 还包括Ce、Sc等, 4个产地羊乳中Ce、Sc元素平均含量均较低(<0.100 mg/kg), 故对产地区分贡献较大的元素为Se、B、Ni, 此模型的判别准确率为87.80%, 而渭南市的准确率为100%, 与数据降维前模型结果一致。
为了验证构建模型的判别能力, 6个渭南市富平县山羊乳样品按照1.3进行处理, 将数据分别导入组I和组II的OPLS-DA模型中, 结果见图6。元素为26种时, 组I 3D得分图(图6A)和组II 3D得分图(图6B)显示预测样品均能很好的归属于正确组内, 验证准确率为100%, 说明建立的模型可有效实现渭南市富平县山羊乳小尺度地域的精准鉴别。
本研究采用微波消解与电感耦合等离子体质谱法, 对宝鸡市、汉中市、咸阳市泾阳县、咸阳市乾县、渭南市、西安市、延安市7个产地羊乳中42种元素进行检测, 结果显示, 羊乳中K、Ca、Fe、Zn、Si、Na的含量较高(>10 mg/kg), 其次是B、Ti、Mg、Al、Cu、Ba (1~10 mg/kg), 其他元素含量相对较低。7个产地羊乳分别采用PCA与OPLS-DA模型分析, 只能将汉中市样品区分开, 汉中市与其他6个地区的地理位置明显不同, 导致汉中市羊乳中Se和Ti等元素含量与其他地区存在差异。
按距离将产地分为组I (150~300 km, 宝鸡市、汉中市、渭南市、延安市)、组II (40~100 km, 咸阳市泾阳县、咸阳市乾县、渭南市、西安市)两组, 分别采用OPLS-DA模型分析, 两模型准确率分别为95.12%、87.80%。其中, 组I羊乳得以区分的主要因素为Ba、Mn、Si、Zn、Se、Na、B元素含量差异, 组II羊乳得以区分的主要因素为Se、B、Ni元素含量差异, 由于地理位置和环境条件不同, 导致饲草、水源等元素种类及含量存在差异, 由此进一步引起不同产地羊乳样品中元素成分及含量的差异, 从而实现产地的区分。渭南市富平县羊乳在组I和组II两模型中的判别准确率均为100%, 该地区羊乳中某些元素含量(Se、B、Ni等)与其他地区存在差异, 可实现准确判别。
对比之前相关的报道[31-32], 本研究建立的多元素分析结合化学计量学方法, 可实现小尺度(50 km以上)范围内对富平山羊乳的准确识别, 这对保护地理标志产品、维护消费者权益以及实现小尺度地域上的产地溯源具有重要意义。
  • 国家重点研发计划项目(2023YFF1104702)
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2025年第16卷第12期
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doi: 10.19812/j.cnki.jfsq11-5956/ts.20241231001
  • 接收时间:2024-12-31
  • 首发时间:2026-01-13
  • 出版时间:2025-06-25
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  • 收稿日期:2024-12-31
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国家重点研发计划项目(2023YFF1104702)
作者信息
    1 中国质量检验检测科学研究院农产品安全研究中心, 北京 100176
    2 国家市场监督管理总局重点实验室(食品真实性鉴别), 北京 100176

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*张紫娟(1974—), 女, 博士, 副研究员, 主要研究方向为食品安全和食品真实性检测。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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