光学学报, 2016, 36 (12): 1230001, 网络出版: 2016-12-14   

拉曼光谱结合多变量统计方法在无损区分寿山石和老挝石中的应用 下载: 515次

Nondestructive Discrimination of Shoushan Stone and Laos Stone Based on Raman Spectroscopy and Multivariate Methods
作者单位
1 上海交通大学大学电子信息与电气工程学院仪器系, 上海 200240
2 上海智能诊疗仪器工程技术研究中心, 上海 200240
3 上海交通大学物理与天文系, 上海 200240
摘要
利用自行研制的便携式拉曼光谱仪(Hx-Spec)对高山石类寿山石(13组)和老挝石(22组)进行了分类判别分析。Hx-Spec拉曼光谱仪的激发波长785 nm, 光谱范围200~2700 cm-1, 分辨率6 cm-1。结合主成分分析(PCA)和线性判别分析(LDA)建立多元统计算法模型, 将老挝石从高山石类寿山石中区别出的特异性和灵敏度分别为100%与86.7%, 受试样品工作特征(ROC)曲线下面积为0.977。另外, 加入8个新样品作为验证, 判别正确率为87.5%。研究表明, 自行研制的便携式拉曼光谱仪结合PCA-LDA统计分析方法有望用于区分高山石类寿山石和老挝石。
Abstract
The Raman spectra of 35 stone samples (13 Shoushan stones and 22 Laos stones) are measured by a self-developed portable Raman spectrometer Hx-Spec, which is excited by a 785 nm diode laser and the spectrum range is 200-2700 cm-1 with a resolution of 6 cm-1. A multioariate model is established by combining the principal component analysis (PCA) and the linear discriminant analysis (LDA), a discrimination sensitivity of 86.7% and a specificity of 100% are achieved in separating Laos stone from Shoushan stone, while the performance of corresponding receiver operating characteristic (ROC) curve is 0.977. Besides, a discriminant accuracy achieves 87.5% after 8 new samples are added as a validation. These results demonstrate that the utility of portable Raman spectrometer combined with chemometrics provides a new strategy to discriminate the Shoushan and Laos stones.
参考文献

[1] 黄志明, 汤德平, 林 辉, 等. 近红外光谱分析在寿山石鉴别中的应用[J]. 宝石和宝石学杂志, 2014, 16(5): 34-43.

    Huang Zhiming, Tang Deping, Lin Hui, et al. Near infrared spectroscopy: A new tool to identify different types of larderite[J]. Journal of Gems and Gemmology, 2014, 16(5): 34-43.

[2] 刘卫东, 江国健, 徐家跃, 等. 寿山石矿物组成及其分类的 XRD 研究[J]. 上海应用技术学院学报 (自然科学版), 2009, 9(3): 175-178.

    Liu Weidong, Jiang Guojian, Xu Jiayue, et al. A study of the composition and classification of Shoushan stone by XRD method[J]. Journal of Shanghai Institute of Technology (Natural Science), 2009, 9(3): 175-178.

[3] 吴 彬, 冯安生. 寿山石的 X 射线衍射鉴定法[J]. 矿产保护与利用, 2010(6): 56-57.

    Wu Bin, Feng Ansheng. Identification method of X-ray diffractometry in Shoushan stone[J], Conservation and Utilization of Mineral Resources, 2010(6): 56-57.

[4] 汤德平, 郑丹威, 黄珊珊. “老挝石” 的矿物组成及鉴别研究[J]. 宝石和宝石学杂志, 2015, 17(1): 1-9.

    Tang Deping, Zheng Danwei, Huang Shanshan. Mineral components and identification of Laos stones[J]. Journal of Gems and Gemmology, 2015, 17(1): 1-9.

[5] 王 含, 周征宇, 钟 倩, 等. 电子微探针-X 射线衍射扫描电镜研究老挝石岩石矿物学特征[J]. 岩矿测试, 2016, 35(1): 56-61.

    Wang Han, Zhou Zhengyu, Zhong Qian, et al. Study on petrological and mineralogical characteristics of Laos stone by EPMA-XRD-SEM[J]. Rock and Mineral Analysis, 2016, 35(1): 56-61.

[6] 杨雅秀, 张乃娴. 中国粘土矿物[M]. 北京: 地质出版社, 1994: 21-22.

[7] 祖恩东, 陈大鹏, 张鹏翔. 翡翠B货的拉曼光谱鉴别[J]. 光谱学与光谱分析, 2003, 23(1): 64-66.

    Zu Endong, Chen Dapeng, Zhang Pengxiang. Identification of B jade by Raman spectroscopy[J]. Spectroscopy and Spectral Analysis, 2003, 23(1): 64-66.

[8] 杨晓丹, 施光海, 刘 琰. 新疆和田黑色透闪石质软玉振动光谱特征及颜色成因[J]. 光谱学与光谱分析, 2012, 32(3): 681-685.

    Yang Xiaodan, Shi Guanghai, Liu Yan. Vibrational spectra of black species of hetiannephrite (tremolite jade) and its color genesis[J]. Spectroscopy and Spectral Analysis, 2012, 32(3): 681-685.

[9] 范建良, 郭守国, 刘学良, 等. 拉曼光谱在红宝石检测中的应用研究[J]. 应用激光, 2008, 28(2): 150-154.

    Fan Jianliang, Guo Shouguo, Liu Xueliang, et al. Application of Raman spectroscopy in ruby identification[J]. Applied Laser, 2008, 28(2): 150-154.

[10] 韩孝朕, 郭正也, 康 燕, 等. 拉曼光谱在鸡血石鉴定中的应用[J]. 光学学报, 2015, 35(1): 0130003.

    Han Xiaozhen, Guo Zhengye, Kang Yan, et al. Application of Raman spectroscopy in certification of chicken-blood stones[J]. Acta Optica Sinica, 2015, 35(1): 0130003.

[11] 孙振华, 黄梅珍, 余镇岗, 等. 便携式拉曼光谱仪在寿山石检测中的应用[J]. 光电子·激光, 2015, 26(6): 1152-1156.

    Sun Zhenhua, Huang Meizhen, Yu Zhengang, et al. Portable Raman spectrometer and its application in Shoushan stone detection[J]. Journal of Optoelectronics·Laser, 2015, 26(6): 1152-1156.

[12] 冯尚源, 潘建基, 伍严安, 等. 基于SERS技术结合多变量统计分析胃癌患者血浆拉曼光谱[J]. 中国科学生命科学, 2011, 41(7): 550-557.

    Feng Shangyuan, Pan Jianji, Wu Yan′an, et al. Study on gastric cancer blood plasma based on surface-enhanced Raman spectroscopy combined with multivariate analysis[J]. Scientia Sinica Vitae, 2011, 41(7): 550-557.

[13] Chen L, Wang Y, Liu Nenrong, et al. Near-infrared confocal micro-Raman spectroscopy combined with PCA-LDA multivariate analysis for detection of esophageal cancer[J]. Laser Physics, 2013, 23(6): 065601.

[14] 郭 丽, 张 毅, 吕金燕, 等. 用多元分析方法研究乳腺癌血清的表面增强拉曼光谱[J]. 光谱学与光谱分析, 2013, 33(6): 1553-1556.

    Guo Li, Zhang Yi, Lü Jinyan, et al. Multivariate statistical analysis of serum from breast cancer patients using surface enhanced Raman spectrum[J]. Spectroscopy and Spectral Analysis, 2013, 33(6): 1553-1556.

[15] Júnior P H R, Oliveira K D S, de Almeida C E, et al. FT-Raman and chemometric tools for rapid determination of quality parameters in milk powder: Classification of samples for the presence of lactose and fraud detection by addition of maltodextrin[J]. Food Chemistry, 2016, 196: 584-588.

[16] Almeida M R, Oliveira K D S, Stephani R, et al. Fourier-transform Raman analysis of milk powder: A potential method for rapid quality screening[J]. Journal of Raman Spectroscopy, 2011, 42(7): 1548-1552.

[17] Rubayiza A B, Meurens M. Chemical discrimination of arabica and robusta coffees by Fourier transform Raman spectroscopy[J]. Journal of Agricultural & Food Chemistry, 2005, 53(12): 4654-4659.

[18] 孙振华, 余镇岗, 黄梅珍, 等. 小型化拉曼光谱仪的优化设计及应用[J]. 光电子·激光, 2015, 26(6): 1132-1137.

    Sun Zhenhua, Yu Zhengang, Huang Meizhen, et al. Optimal design of a portable Raman spectrometer and the prediminary applications[J]. Journal of Optoelectronics·Laser, 2015, 26(6): 1132-1137.

[19] Yu Z G, Huang M Z, Wang Y, et al. Fast wavelength calibration method for spectrometers based on waveguide comb optical filter[J]. Review of Scientific Instruments, 2015, 86(4): 043103.

[20] Mokrane A, Friant-Michel P, Cartier A, et al. Scaled semiempirical method for the calculation of vibrational spectra molecular vibrational frequencies of monosaccharides and disaccharides by PM3 method[J]. Journal of Molecular Structure, 1997, 395: 71-80.

[21] Frost R L. Fourier transform Raman spectroscopy of kaolinite, dickite and halloysite[J]. Clays and Clay Minerals, 1995, 43(2): 191-195.

[22] Frost R L, Tran T H, Rintoul L, et al. Raman microscopy of dickite, kaolinite and their intercalates[J]. Analyst, 1998, 123(4): 611-616.

[23] Johnston C T, Helsen J, Schoonheydt R A, et al. Single-crystal Raman spectroscopic study of dickite[J]. American Mineralogist, 1998, 83(1): 75-84.

[24] Haaland D M, Thomas E V. Partial least-squares methods for spectral analyses.1.Relation to other quantitative calibration methods and the extraction of qualitative information[J]. Analytical Chemistry, 1988, 60(11): 1193-1202.

[25] Holmes E, Nicholson J K, Nicholls A W, et al. The identification of novel biomarkers of renal toxicity using automatic data reduction techniques and PCA of proton NMR spectra of urine[J]. Chemometrics and Intelligent Laboratory Systems, 1998, 44(1): 245-255.

李夏, 黄梅珍, 宋彪, 邹烨, 陈婕, 汪洋. 拉曼光谱结合多变量统计方法在无损区分寿山石和老挝石中的应用[J]. 光学学报, 2016, 36(12): 1230001. Li Xia, Huang Meizhen, Song Biao, Zou Ye, Chen Jie, Wang Yang. Nondestructive Discrimination of Shoushan Stone and Laos Stone Based on Raman Spectroscopy and Multivariate Methods[J]. Acta Optica Sinica, 2016, 36(12): 1230001.

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