小麦秸秆中K和Na元素LIBS同步定量分析研究
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摘要
快速分析小麦秸秆中K和Na元素含量对提高其燃烧效率具有重要的现实意义。选用华北地区29个小麦秸秆代表性样本作为研究对象,以电感耦合等离子体质谱法(ICP-MS)量测结果作为标准值,探讨激光诱导击穿光谱(LIBS)技术对小麦秸秆中K和Na元素含量进行定量预测分析的可行性。为提高模型定量分析精度,首先分别选取K和Na分析线附近波段光谱作为定标模型原始光谱数据,对比基线校正(BC)、归一化(Norm)与中心化(MC)相互组合算法对LIBS光谱降噪效果影响,分析比较线性建模方法:偏最小二乘回归(PLSR)和非线性建模方法:增强型反向传播人工神经网络(BP-ADaboost)对预处理后光谱数据的适用性。研究结果发现,与PLSR模型相比较,小麦秸秆中K和Na的BP-ADaboost最优模型效果均较好,其预测决定系数R2p分别为0. 908和0. 979,预测均方根误差分别为2. 388 g/kg和0. 138 g/kg,相对分析误差分别为2. 358和4. 203。结果表明,LIBS技术能用于小麦秸秆中K和Na的同步快速定量分析。
It is of great practical significance to rapidly analyze the content of potassium( K) and sodium( Na) in wheat straw for improving its combustion efficiency. And totally 29 representative wheat straw samples collected from North China were chosen as the research objects. Based on the standard values measured by inductively coupled plasma mass spectrometry( ICP-MS), laser induced breakdown spectroscopy( LIBS) was used for the quantitative analysis of K and Na contents in wheat straw. In order to improve the accuracy of quantitative analysis,the spectral bands around the analytical lines of K and Na were primarily confirmed as original spectral data of the calibration models,respectively. The effects of baseline correction( BC),normalization( Norm) and mean-centering( MC) on LIBS spectral denoising were compared. Moreover,the applicability of partial least squares regression( PLSR) and Adaboost backpropagation artificial neural network( BP-ADaboost) for preprocessed spectral data was compared and analyzed. Results showed that when compared with PLSR models,the BP-ADaboost models of potassium and sodium in wheat straw both had better effects,yielding R2 pof 0. 908 and 0. 979,root mean square error of prediction set of 2. 388 g/kg and 0. 138 g/kg,relative percent deviation of2. 358 and 4. 203,respectively. Therefore,LIBS technique can be used for the simultaneous quantitative analysis of K and Na in wheat straw.
It is of great practical significance to rapidly analyze the content of potassium( K) and sodium( Na) in wheat straw for improving its combustion efficiency. And totally 29 representative wheat straw samples collected from North China were chosen as the research objects. Based on the standard values measured by inductively coupled plasma mass spectrometry( ICP-MS), laser induced breakdown spectroscopy( LIBS) was used for the quantitative analysis of K and Na contents in wheat straw. In order to improve the accuracy of quantitative analysis,the spectral bands around the analytical lines of K and Na were primarily confirmed as original spectral data of the calibration models,respectively. The effects of baseline correction( BC),normalization( Norm) and mean-centering( MC) on LIBS spectral denoising were compared. Moreover,the applicability of partial least squares regression( PLSR) and Adaboost backpropagation artificial neural network( BP-ADaboost) for preprocessed spectral data was compared and analyzed. Results showed that when compared with PLSR models,the BP-ADaboost models of potassium and sodium in wheat straw both had better effects,yielding R2 pof 0. 908 and 0. 979,root mean square error of prediction set of 2. 388 g/kg and 0. 138 g/kg,relative percent deviation of2. 358 and 4. 203,respectively. Therefore,LIBS technique can be used for the simultaneous quantitative analysis of K and Na in wheat straw.
引文
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[18]张贵银,季慧,靳一东.样品的激光诱导击穿光谱及谱线的自吸收现象[J].光谱学与光谱分析,2014,34(12):3397-3400.ZHANG Guiyin,JI Hui,JIN Yidong. Laser induced breakdown spectra of coal sample and self-absorption of the spectral line[J]. Spectroscopy and Spectral Analysis,2014,34(12):3397-3400.(in Chinese)
[19]胡慧琴,徐雪红,刘木华,等.激光诱导击穿光谱结合偏最小二乘法直接检测皮蛋壳中的Cu含量[J].光谱学与光谱分析,2015,35(12):3500-3504.HU Huiqin,XU Xuehong,LIU Muhua,et al. Determination of Cu in shell of preserved egg by LIBS coupled with PLS[J].Spectroscopy and Spectral Analysis,2015,35(12):3500-3504.(in Chinese)
[20]郭明才.原子吸收光谱分析应用指南[M].青岛:中国海洋大学出版社,2012.
[2] FANG X,AHMAD S R. Elemental analysis in environmental land samples by stand-off laser-induced breakdown spectroscopy[J]. Applied Physics B,2014,115(4):497-503.
[3] HADDAD J E,BRUYERE D,ISMAEL A,et al. Application of a series of artificial neural networks to on-site quantitativeanalysis of lead into real soil samples by laser induced breakdown spectroscopy[J]. Spectrochimica Acta Part B:AtomicSpectroscopy,2014,97(7):57-64.
[4] KRAJCAROVA L,NOVOTNY K,BABULA P,et al. Copper transport and accumulation in spruce stems(Picea abies(L.)Karsten)revealed by laser-induced breakdown spectroscopy[J]. International Journal of Electrochemical Science,2013,8(4):4485-4504.
[5] KRYSTOFOVA O,SHESTIVSKA V,GALIOVA M,et al. Sunflower plants as bioindicators of environmental pollution with lead(Ⅱ)ions[J]. Sensors,2009,9(7):5040-5058.
[6] KUMAR R,TRIPATHI D K,DEVANATHAN A,et al. In-situ monitoring of chromium uptake in different parts of the wheatseedling(Triticum aestivum)using laser-induced breakdown spectroscopy[J]. Spectroscopy Letters,2014,47(7):554-563.
[7] TREVIZAN L C,SANTOS D,SAMAD R E,et al. Evaluation of laser induced breakdown spectroscopy for the determination ofmicronutrients in plant materials[J]. Spectrochimica Acta Part B:Atomic Spectroscopy,2009,64(5):369-377.
[8] MA S,GAO X,GUO K,et al. Analysis of the element content in poplar tree leaves by femtosecond laser-induced breakdownspectroscopy[J]. Science China(Physics Mechanics&Astronomy),2011,54(11):1953-1957.
[9] BRAGA J W B,TREVIZAN L C,NUNES L C,et al. Comparison of univariate and multivariate calibration for thedetermination of micronutrients in pellets of plant materials by laser induced breakdown spectrometry[J]. Spectrochimica ActaPart B:Atomic Spectroscopy,2010,65(1):66-74.
[10] KIM G,KWAK J,CHOI J,et al. Detection of nutrient elements and contamination by pesticides in spinach and rice samplesusing laser-induced breakdown spectroscopy(LIBS)[J]. Journal of Agricultural and Food Chemistry,2012,60(3):718-724.
[11] LEI W Q,HADDAD J E,MOTTO-ROS V,et al. Comparative measurements of mineral elements in milk powders with laser-induced breakdown spectroscopy and inductively coupled plasma atomic emission spectroscopy[J]. Analytical and BioanalyticalChemistry,2011,400(10):3303-3313.
[12] DUAN H,MA S,HAN L,et al. A novel denoising method for laser-induced breakdown spectroscopy:improved wavelet dualthreshold function method and its application to quantitative modeling of Cu and Zn in Chinese animal manure composts[J].Microchemical Journal,2017,134:262-269.
[13] HOEHSE M,PAUL A,GORNUSHKIN I,et al. Multivariate classification of pigments and inks using combined Ramanspectroscopy and LIBS[J]. Analytical and bioanalytical chemistry,2012,402(4):1443-1450.
[14] ZHANG T,WU S,DONG J,et al. Quantitative and classification analysis of slag samples by laser induced breakdownspectroscopy(LIBS)coupled with support vector machine(SVM)and partial least square(PLS)methods[J]. Journal ofAnalytical Atomic Spectrometry,2015,30(2):368-374.
[15]董春旺,赵杰文,朱宏凯,等.基于RSM和BP-AdaBoost-GA的红茶发酵性能参数优化[J/OL].农业机械学报,2017,48(5):335-342.DONG Chunwang,ZHAO Jiewen,ZHU Hongkai,et al. Parameter optimization of black tea fermentation machine based onRSM and BP-AdaBoost-GA[J/OL]. Transactions of the Chinese Society for Agricultural Machinery,2017,48(5):335-342.http:∥www. j-csam. org/jcsam/ch/reader/view_abstract. aspx? file_no=20170542&flag=1&journal_id=jcsam. DOI:10.6041/j. issn. 1000-1298. 2017. 05. 042.(in Chinese)
[16] MALLEY D F,MCCLURE C,MARTIN P D,et al. Compositional analysis of cattle manure during composting using a field-portable near-infrared spectrometer[J]. Communications in Soil Science&Plant Analysis,2005,36(4-6):455-475.
[17]张俊宁,方宪法,张小超,等.基于激光诱导击穿光谱的土壤钾素检测[J/OL].农业机械学报,2014,45(10):294-299.ZHANG Junning,FANG Xianfa,ZHANG Xiaochao,et al. Detection of soil potassium content based on laser-inducedbreakdown spectroscopy[J/OL]. Transactions of the Chinese Society for Agricultural Machinery,2014,45(10):294-299.http:∥www. j-csam. org/ch/reader/view_abstract. aspx? file_no=20141046&flag=1&journal_id=jcsam. DOI:10. 6041/j.issn. 1000-1298. 2014. 10. 046.(in Chinese)
[18]张贵银,季慧,靳一东.样品的激光诱导击穿光谱及谱线的自吸收现象[J].光谱学与光谱分析,2014,34(12):3397-3400.ZHANG Guiyin,JI Hui,JIN Yidong. Laser induced breakdown spectra of coal sample and self-absorption of the spectral line[J]. Spectroscopy and Spectral Analysis,2014,34(12):3397-3400.(in Chinese)
[19]胡慧琴,徐雪红,刘木华,等.激光诱导击穿光谱结合偏最小二乘法直接检测皮蛋壳中的Cu含量[J].光谱学与光谱分析,2015,35(12):3500-3504.HU Huiqin,XU Xuehong,LIU Muhua,et al. Determination of Cu in shell of preserved egg by LIBS coupled with PLS[J].Spectroscopy and Spectral Analysis,2015,35(12):3500-3504.(in Chinese)
[20]郭明才.原子吸收光谱分析应用指南[M].青岛:中国海洋大学出版社,2012.
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