基于矿质元素指纹分析的陈皮产地溯源研究

Study on Origin Tracing of Dried Tangerine Peel Using Mineral Element Fingerprints

通过分析不同产地陈皮中矿质元素含量的差异,结合多元统计分析,筛选基于矿质元素指纹分析技术的有效产地溯源指标,构建陈皮不同产地鉴别的判别模型。该研究采集了广东、福建、重庆3个不同产地的206份陈皮样品,利用电感耦合等离子体质谱仪(ICP-MS)和电感耦合等离子体发射光谱仪(ICP-AES)测定了32种矿质元素含量,结合方差分析、主成分分析和线性判别分析、正交-偏最小二乘法判别分析方法建立了陈皮产地判别模型。结果表明,陈皮样品的32种矿质元素中有26种元素含量在广东与其他两个产地间存在显著差异,而其中11种元素在3个不同产地间存在显著差异。经过主成分分析,从32种矿质元素可提取出4个主成分,代表了总指标70.0%的信息。基于主成分分析,陈皮样品可根据其来源进行初步聚类。其中前2个主成分的主要变量为Dy、Sm、Gd、Pr、Nd、Y、La、Fe、Be、V、Ce、Sc、Co、P、Mo、As、Pb、B这18种元素。通过线性判别分析确定了K、P、Ca、Co、Cu、Mn、Mo、V、Ni、B、Li、Pb、As、Sr、Ti、Th、Gd、Sc、Nd、Pr、Y这21种矿质元素为陈皮的有效溯源指标,基于正交-偏最小二乘法判别分析方法建立的判别模型确定了Sc、B、Y、Co、Nd、La、Pr、Be、Gd、Dy、Sm、Mo、Fe这13种元素的重要性。2种判别分析方法构建的判别模型的交叉验证和外部样品验证的整体正确判别率均达到100%,基本实现了陈皮的产地判别,研究证明矿质元素指纹分析技术可用于陈皮的产地溯源判别。

By analyzing the differences of mineral element contents in dried tangerine peel from different producing areas,combined with multivariate statistical analysis,the effective origin traceability indexes based on mineral element fingerprint analysis technology were selected to construct its discrimination model of different origin identification.In this study,206 dried tangerine peel samples were collected from three different producing areas as Guangdong,Fujian and Chongqing.The contents of 32 mineral elements were determined by inductively coupled plasma mass spectrometer(ICP-MS)and inductively coupled plasma atomic emission spectrometer(ICP-AES).Combined with analysis of variance,principal component analysis,linear discriminant analysis and orthogonal partial least squares discriminant analysis,a discriminant model of dried tangerine peel producing area was established.The results showed that 26 of the 32 mineral elements in the dried tangerine peel samples had significant differences between Guangdong and other two producing areas,and 11 of them had significant differences between the three different regions.After principal component analysis,four principal components could be extracted from the 32 mineral elements,representing 70.0%of the total index.Based on the principal component analysis,the dried tangerine peel samples could be preliminarily clustered according to their different origin.The main variables of the first two principal components were Dy,Sm,Gd,Pr,Nd,Y,La,Fe,Be,V,Ce,Sc,Co,P,Mo,As,Pb and B.Through linear discriminant analysis,21 mineral elements K,P,Ca,Co,Cu,Mn,Mo,V,Ni,B,Li,Pb,As,Sr,Ti,Th,Gd,Sc,Nd,Pr and Y were determined as effective traceability indexes of the dried tangerine peel.Additionally,based on the discriminant model established by orthogonal partial least squares discriminant analysis,the importance of 13 elements Sc,B,Y,Co,Nd,La,Pr,Be,Gd,Dy,Sm,Mo and Fe were determined.For the discrimination models established by the two above-mentioned discrimination analysis methods,their overall correct discrimination rates of cross validation and external sample validation were both 100%,which basically achieved the origin discrimination of dried tangerine peel.The research suggested that the mineral element fingerprint analysis technology can be used for the origin traceability discrimination of dried tangerine peel.