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烟草样品中微量金属元素含量测定及模式识别研究
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摘要
烟草生长过程中需要多种微量元素以维持正常的生命活动,这些微量元素共同影响着烟草质量和产量。但是烟草又容易富集一些有害元素于烟叶内,特别是一些重金属元素会危害人体健康。烟草内微量元素含量与烟草质量关系密不可分,与人体健康关系更是不容忽视。烟草中微量金属元素的测定,可以为烟草培育和吸烟与健康提供烟草中微量金属元素含量的信息。
     烟草在生长过程中由于地理环境和田间管理技术不同导致烟叶内微量元素的差异。因此,烟草样品中微量元素含量可以为判别样品的产地、来源和类别提供非常有用的信息。基于微量元素含量信息对烟草进行分类,有助于追溯烟草类别和产地,为烟草的质量控制提供科学的依据。论文的主要内容包括:
     1.综述了微量元素含量对烟草质量和人体健康的影响,介绍了目前植物样品中微量元素含量检测的主要的分析技术,对电感耦合等离子体质谱技术做了详细应用介绍。介绍了植物样品分类常用的模式识别技术,主要概述了聚类分析和支持向量机分类的应用。
     2.对烟草样品前处理方法进行了改进,以钛(Ti)、镍(Ni)、铜(Cu)、铷(Rb)、锶(Sr)、钇(Y)、锑(Sb)、铊(Tl)8个金属元素测定结果作为考核指标。采用2 mL 50% HNO3和1 mL 47 % H2O2作为消解体系对烟草样品进行微波消解,最终消解液酸度在2%左右,标准溶液采用2% HNO3稀释,添加Ge、Rh内标元素,进行ICP - MS分析。该方法与其他消解处理方法相比,可省去赶酸或稀释的繁琐步骤,延长仪器相关部件使用寿命,减小由于样品溶液与标准溶液酸度差别较大带来的误差,检出限为0.006 - 1.133 ng/mL,相对标准偏差0.90% - 5.66%,回收率93% - 102%。结果表明,本文所提出的微波消解方法适用于烟草中多种微量元素的同时测定。并将此方法应用于测定6个产地的88个烟草样品中44种微量元素含量,得到了88个烟草样品中44种微量元素含量。为烟草栽培、烟草与人体健康提供更全面的微量元素含量信息。由检测结果,看出烟草中微量元素含量与烟草来源有一定的关联性。
     3.以微量元素含量信息作为特征值,采用模糊c -均值聚类分析(FCM)进行烟草样品聚类。结果表明,在不含山东样本和稀土元素含量属性的情况下,基于微量元素含量的FCM聚类分析结果与烟草产地有着很好的对应和匹配。河南、四川两地准确度达100%,福建地区准确度88.89%,云南地区准确度80.00%;用包含稀土元素含量在内的全部测定金属元素含量进行FCM聚类分析,总体预报准确率偏低。说明在进行烟草FCM聚类分析时,特征元素的选择对成功分类的重要性。
     4.将支持向量机(SVM classification)分类应用于不同产地烟草样本分类预测,以44种微量元素含量信息作为输入特征值,以不同产地来源作为相应的输出。结果表明,在所有烟草样本和微量元素都参与的情况下,SVM分类预测准确度达90%,在考虑了烟草样本和稀土元素含量影响情况下,SVM分类预测准确度达可以提高到92.59%。结果表明SVM分类模型性能优良,预测精度高,具有强大泛化能力。优于FCM,可应用于烟草样品来源的分类和预测。
Tobaccos need kinds of trace elements for its life activities, and they influence the quality and yield of the tobaccos corporately. But tobacco plants very easily take up some toxic elements and concentrate them in leaves, specially some heavy metal elements which are harmful to human health. There is a deep relationship between the contents of trace elements in tobaccos and quality of tobaccos, and the relationship between the contents of trace elements in tobaccos and human health is also indispensable. Determination of trace metal elements in tobaccos provide the information of trace elements contents for cultivation of tobaccos and smoking and health and a scientific basis for quality control of tobaccos.
     The trace elements contents differ in different kinds of tobaccos due to the different geographical origin and the way of cultivation, and therefore the contents of trace elements can be very useful as markers for identification of the product’s geographical origin and authenticity. Classification of tobaccos based on their contents of trace elements is helpful for identification of tobacco classes and geographical origin. The main contents of this dissertation are as followings:
     1. The influence of contents of trace elements on tobaccos quality and human health was reviewed. The popular analysis techniques of determation of trace elements in plant were introudced, specially a detailed introduction of the applation of inductively coupled plasma mass spectrometry technique was gave. Pattern recognition technique as a normal classfication technique for plant samples was introduced and the application of clustering analysis and SVM classification was mainly summarized.
     2. The method of tobaccos sample pretreatment was improved. The result of eight elements was used as examination index. There was Ti, Ni, Cu, Rb, Sr, Y, Sb, Tl. 2 mL 50% HNO3 and 1 mL 47% H2O2 were chosen for tobaccos digestion, and the acidity of final digestion solution was confined to about 2%. Standard solutions were diluted with 2% HNO3. The digestion solutions were determined by ICP - MS directly after adding internal standard elements Ge and Rh. Compared with other digestion menthods, this method not only can save the process of drying or dilution and extended the life of relevant components of the instrument, but also the errors of the inconsistency between digestion solutions and standard solutions could be reduced. The detection limits were 0.006 - 1.133 ng/mL. The relative standard deviations were 0.90% - 5.66%. The recovery rates were 93% - 102%. The results showed that this method proposed could be applied to multielement simultaneous determination of tobaccos. The improved method was applied to determine the contents of 44 trace elements in 88 tobaccos from six areas. The contents of 44 trace elements in 88 tobaccos sample were got, and the results can provide more comprehensive informations of trace elements for cultivation of tobaccos and smoking and health. From the results, we found there had certain relevance between the contents of trace elements in tobaccos and the geographical origin.
     3. Fuzzy c - means (FCM) was used for classification of the different kinds of tobaccos based on the contents of trace elements. The results show that there was a good correspondence between the results of FCM clustering analysis and the geographical origin of the tobaccos, when the samples from Shandong Provice and the contents of the rare earth elements were removed. The accuracy of Henan and Sichuan area reached 100%. The accuracy of Fujian and Yunnan area were 88.89% and 80.00% respectively. But the accuracy was low when all the testing results including rare earth elements were employed for FCM clustering analysis. It indicated that selection of characteristic elements was important for successful classification when FCM clustering analysis was used for tobaccos classification.
     4. Support vector machine (SVM) classification was introduced for classification and prediction of the tobaccos sample from different origin. The contents of 44 trace elements were input features and the corresponding output were the diffrerent origin of the tobaccos. The results showed that the accuracy of the prediction reached 90%, when all the tobaccos sample and trace elements were involved. The accuracy of the prediction could be improved to 92.59%, when the influence of uniformity of the samples and the contents of the rare earth elements were considered. The results demonstrated that the SVM classifier has an excellent performance, high accuracy of the prediction, and powerful generalization capability. SVM classification was superior to FCM analysis, and it could be applied to classification and prediction of tobaccos.
引文
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