Tingting Chen, Jiaqiang Du, Tianlong Zhang, Hua Li
{"title":"基于光纤准直系统激光诱导击穿光谱信号增强的微米级单粒子多元素定量分析","authors":"Tingting Chen, Jiaqiang Du, Tianlong Zhang, Hua Li","doi":"10.1021/acs.analchem.4c05221","DOIUrl":null,"url":null,"abstract":"With rapid, energy-intensive, and coal-fueled economic growth, global air quality is deteriorating, and particulate matter pollution has emerged as one of the major public health problems worldwide. It is extremely urgent to achieve carbon emission reduction and air pollution prevention and control, aiming at the common problem of weak and unstable signals of characteristic elements in the application of laser-induced breakdown spectroscopy (LIBS) technology for trace element detection. In this study, the influence of the optical fiber collimation signal enhancement method on the LIBS signal was explored. Then, the influence of the LIBS signal enhancement system based on an optical fiber collimated system on LIBS spectral signal intensity and signal-to-noise ratio (SNR) was compared, and the influences of different spectral preprocessing methods and different variable selection methods on the prediction performance of the random forest (RF) calibration model were investigated. Finally, the Savitzky–Golay convolution derivative (SG)-variable importance projection (VIP)-mutual information (MI)-RF (Zn), first-order derivative (D1st)-variable importance measurement (VIM)-successive projections algorithm (SPA)-RF (Cu), and D1st-VIM-MI-RF (Ni) optimal models were constructed according to the optimal spectral preprocessing method and the optimal hybrid variable selection method. The prediction performances of their optimal RF model after SG-VIP-MI (Zn), D1st-VIM-SPA (Cu), and D1st-VIM-MI (Ni) spectral preprocessing and hybrid variable selection method are presented as follows: Zn (<i>R</i><sub>p</sub><sup>2</sup> = 0.9860; MREP = 0.0590), Cu (<i>R</i><sub>p</sub><sup>2</sup> = 0.9817; MREP = 0.0405), and Ni (<i>R</i><sub>p</sub><sup>2</sup> = 0.9856; MREP = 0.0875). The above results demonstrate that the RF calibration model based on the optical fiber collimated LIBS signal enhancement method, the optimal spectral preprocessing method, and variable selection strategy overcome the key problems of low SNR and low quantitative accuracy in single particle detection. It is expected to provide a theoretical basis and technical support for in situ online rapid monitoring of particulate matter.","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":"49 1","pages":""},"PeriodicalIF":6.7000,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Quantitative Analysis of Multi-Elements in a Micron-Sized Single Particle Based on Laser-Induced Breakdown Spectroscopy Signal Enhancement of an Optical Fiber Collimated System\",\"authors\":\"Tingting Chen, Jiaqiang Du, Tianlong Zhang, Hua Li\",\"doi\":\"10.1021/acs.analchem.4c05221\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"With rapid, energy-intensive, and coal-fueled economic growth, global air quality is deteriorating, and particulate matter pollution has emerged as one of the major public health problems worldwide. It is extremely urgent to achieve carbon emission reduction and air pollution prevention and control, aiming at the common problem of weak and unstable signals of characteristic elements in the application of laser-induced breakdown spectroscopy (LIBS) technology for trace element detection. In this study, the influence of the optical fiber collimation signal enhancement method on the LIBS signal was explored. Then, the influence of the LIBS signal enhancement system based on an optical fiber collimated system on LIBS spectral signal intensity and signal-to-noise ratio (SNR) was compared, and the influences of different spectral preprocessing methods and different variable selection methods on the prediction performance of the random forest (RF) calibration model were investigated. Finally, the Savitzky–Golay convolution derivative (SG)-variable importance projection (VIP)-mutual information (MI)-RF (Zn), first-order derivative (D1st)-variable importance measurement (VIM)-successive projections algorithm (SPA)-RF (Cu), and D1st-VIM-MI-RF (Ni) optimal models were constructed according to the optimal spectral preprocessing method and the optimal hybrid variable selection method. The prediction performances of their optimal RF model after SG-VIP-MI (Zn), D1st-VIM-SPA (Cu), and D1st-VIM-MI (Ni) spectral preprocessing and hybrid variable selection method are presented as follows: Zn (<i>R</i><sub>p</sub><sup>2</sup> = 0.9860; MREP = 0.0590), Cu (<i>R</i><sub>p</sub><sup>2</sup> = 0.9817; MREP = 0.0405), and Ni (<i>R</i><sub>p</sub><sup>2</sup> = 0.9856; MREP = 0.0875). The above results demonstrate that the RF calibration model based on the optical fiber collimated LIBS signal enhancement method, the optimal spectral preprocessing method, and variable selection strategy overcome the key problems of low SNR and low quantitative accuracy in single particle detection. 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引用次数: 0
摘要
随着能源密集型和以煤炭为燃料的经济快速增长,全球空气质量正在恶化,颗粒物污染已成为全球主要的公共卫生问题之一。针对应用激光诱导击穿光谱(LIBS)技术进行微量元素检测时常见的特征元素信号微弱、不稳定的问题,实现碳减排和大气污染防治迫在眉睫。本研究探讨了光纤准直信号增强方法对LIBS信号的影响。然后,比较了基于光纤准直系统的LIBS信号增强系统对LIBS光谱信号强度和信噪比的影响,并研究了不同的光谱预处理方法和不同的变量选择方法对随机森林(RF)校准模型预测性能的影响。最后,根据最优光谱预处理方法和最优混合变量选择方法,构建Savitzky-Golay卷积导数(SG)-可变重要度投影(VIP)-互信息(MI)-RF (Zn)、一阶导数(d1)-可变重要度测量(VIM)-连续投影算法(SPA)-RF (Cu)和d1 -VIM-MI-RF (Ni)最优模型。经SG-VIP-MI (Zn)、d1 - vim - spa (Cu)和d1 - vim - mi (Ni)光谱预处理和混合变量选择方法后,其最优RF模型的预测性能如下:Zn (Rp2 = 0.9860;MREP = 0.0590), Cu (Rp2 = 0.9817;MREP = 0.0405), Ni (Rp2 = 0.9856;Mrep = 0.0875)。上述结果表明,基于光纤准直LIBS信号增强方法的射频校准模型、最优光谱预处理方法和变量选择策略克服了单粒子检测中信噪比低和定量精度低的关键问题。有望为颗粒物的现场在线快速监测提供理论依据和技术支持。
Quantitative Analysis of Multi-Elements in a Micron-Sized Single Particle Based on Laser-Induced Breakdown Spectroscopy Signal Enhancement of an Optical Fiber Collimated System
With rapid, energy-intensive, and coal-fueled economic growth, global air quality is deteriorating, and particulate matter pollution has emerged as one of the major public health problems worldwide. It is extremely urgent to achieve carbon emission reduction and air pollution prevention and control, aiming at the common problem of weak and unstable signals of characteristic elements in the application of laser-induced breakdown spectroscopy (LIBS) technology for trace element detection. In this study, the influence of the optical fiber collimation signal enhancement method on the LIBS signal was explored. Then, the influence of the LIBS signal enhancement system based on an optical fiber collimated system on LIBS spectral signal intensity and signal-to-noise ratio (SNR) was compared, and the influences of different spectral preprocessing methods and different variable selection methods on the prediction performance of the random forest (RF) calibration model were investigated. Finally, the Savitzky–Golay convolution derivative (SG)-variable importance projection (VIP)-mutual information (MI)-RF (Zn), first-order derivative (D1st)-variable importance measurement (VIM)-successive projections algorithm (SPA)-RF (Cu), and D1st-VIM-MI-RF (Ni) optimal models were constructed according to the optimal spectral preprocessing method and the optimal hybrid variable selection method. The prediction performances of their optimal RF model after SG-VIP-MI (Zn), D1st-VIM-SPA (Cu), and D1st-VIM-MI (Ni) spectral preprocessing and hybrid variable selection method are presented as follows: Zn (Rp2 = 0.9860; MREP = 0.0590), Cu (Rp2 = 0.9817; MREP = 0.0405), and Ni (Rp2 = 0.9856; MREP = 0.0875). The above results demonstrate that the RF calibration model based on the optical fiber collimated LIBS signal enhancement method, the optimal spectral preprocessing method, and variable selection strategy overcome the key problems of low SNR and low quantitative accuracy in single particle detection. It is expected to provide a theoretical basis and technical support for in situ online rapid monitoring of particulate matter.
期刊介绍:
Analytical Chemistry, a peer-reviewed research journal, focuses on disseminating new and original knowledge across all branches of analytical chemistry. Fundamental articles may explore general principles of chemical measurement science and need not directly address existing or potential analytical methodology. They can be entirely theoretical or report experimental results. Contributions may cover various phases of analytical operations, including sampling, bioanalysis, electrochemistry, mass spectrometry, microscale and nanoscale systems, environmental analysis, separations, spectroscopy, chemical reactions and selectivity, instrumentation, imaging, surface analysis, and data processing. Papers discussing known analytical methods should present a significant, original application of the method, a notable improvement, or results on an important analyte.