Quantification of major elements in limestones using laser-induced breakdown spectroscopy combined with multivariate regression approaches
CHEN Junxi1, CHEN Sha2, YANG Yanting3, WANG Xu*2 DUAN Yixiang*2
1. School of Chemical Engineering,Sichuan University,Chengdu 610065,China; 2. School of Mechanical Engineering,Sichuan University,Chengdu 610065,China; 3. Chengdu Aliben Science & Technology Co.,LTD.,Chengdu 610000,China
Abstract：Limestones had been widely used in metallurgy,manufacturing,chemistry,architecture,etc.in recent years due to its excellent mineralogical properties.The carbonate and non-carbonate components,such as CaO,SiO2,Fe2O3 and MgO,played important roles in the industrial application of limestones.Therefore,in order to achieve accurate quantification of the components above in limestones and maximize their commercial value,the quantitative analysis of four major elements including Ca,Si,Fe and Mg was investigated based on a portable laser-induced breakdown spectrometer (LIBS) combined with univariate model,partial least square regression and principal component regression.The results of cross validation were used as the criteria for parameter optimization of multivariate regression models.The predictive determination coefficient,the root mean square error of prediction and the relative standard deviation of test set were applied to evaluate the quantitative accuracy and stability of these three regression models.The results showed that the multivariate regression methods improved the quantitative performance of traditional univariate analysis significantly.Among them,the principal component regression performed best.The four elements achieved the predictive determination coefficient of 0.999 8,0.999 6,0.999 6 and 0.999 0,and the root mean square errors of prediction of 0.066 6%,0.089 3%,0.014 8% and 0.038 9%,respectively,and the relative standard deviations of 1.00%,5.04%,5.03% and 13.18%,respectively.It was indicated that the multivariate regression model could not only correct the quantitative accuracy deviation of traditional univariate analysis caused by matrix effects and spectral line interference,but also adjust the detection instability caused by environment,hardware system and samples.Furthermore,principal component regression could be a reliable method for the portable LIBS quantitative analysis of major elements in limestone samples.
陈君玺, 陈莎, 杨燕婷, 王旭, 段忆翔. 激光诱导击穿光谱结合多变量回归法对石灰岩中主量元素的定量分析[J]. 冶金分析, 2021, 41(1): 13-23.
CHEN Junxi, CHEN Sha, YANG Yanting, WANG Xu DUAN Yixiang. Quantification of major elements in limestones using laser-induced breakdown spectroscopy combined with multivariate regression approaches. , 2021, 41(1): 13-23.
Fahad M,Iqbal Y,Riaz M,et al.Metamorphic temperature investigation of coexisting calcite and dolomite marble——examples from Nikani Ghar marble and Nowshera Formation,Peshawar Basin,Pakistan[J].Journal of Earth Science,2016,27(6):989-997.
[2]
Hahn D W,Omenetto N.Laser-induced breakdown spectroscopy (LIBS),part I:review of basic diagnostics and plasma-particle interactions:still-challenging issues within the analytical plasma community[J].Applied Spectroscopy,2010,64(12):335A-366A.
[3]
Peter L,Sturm V,Noll R.Liquid steel analysis with laser-induced breakdown spectrometry in the vacuum ultraviolet[J].Applied Optics,2003,42(30):6199-6204.
[4]
Rai A K,Yueh F Y,Singh J P,et al.High temperature fiber optic laser-induced breakdown spectroscopy sensor for analysis of molten alloy constituents[J].Review of Scientific Instruments,2002,73(10):3589-3599.
[5]
Liang L,Zhang T,Wang K,et al.Classification of steel materials by laser-induced breakdown spectroscopy coupled with support vector machines[J].Applied Optics,2014,53(4):544-552.
[6]
Zhang H,Singh J P,Yueh F Y,et al.Laser-induced breakdown spectra in a coal-fired MHD facility[J].Applied Spectroscopy,1995,49(11):1617-1623.
[7]
Ottesen D,Wang J,Radziemski L.Real-time laser spark spectroscopy of particulates in combustion environments[J].Applied Spectroscopy,1989,43(6):967-976.
[8]
Forni O,Maurice S,Gasnault O,et al.Independent component analysis classification of laser induced breakdown spectroscopy spectra[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2013,86:31-41.
[9]
Death D,Cunningham A,Pollard L.Multi-element analysis of iron ore pellets by laser-induced breakdown spectroscopy and principal components regression[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2008,63(7):763-769.
[10]
Ollila A M,Lasue J,Newsom H E,et al.Comparison of two partial least squares-discriminant analysis algorithms for identifying geological samples with the ChemCam laser-induced breakdown spectroscopy instrument[J].Applied Optics,2012,51(7):B130-B142.
[11]
Yelameli M,Thornton B,Takahashi T,et al.OCEANS 2016-Shanghai:Support vector machine based classification of seafloor rock types measured underwater using laser induced breakdown spectroscopy[C]//Shanghai:[s.n],2016:1-4.
[12]
Sirven J B,Salle B,Mauchien P,et al.Feasibility study of rock identification at the surface of Mars by remote laser-induced breakdown spectroscopy and three chemometric methods[J].Journal of Analytical Atomic Spectrometry,2007,22(12):1471-1480.
[13]
lvarez C,Pisonero J,Bordel N.Quantification of fluorite mass-content in powdered ores using a laser-induced breakdown spectroscopy method based on the detection of minor elements and CaF molecular bands[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2014,100:123-128.
[14]
Li X,Yang S,Fan R,et al.Discrimination of soft tissues using laser-induced breakdown spectroscopy in combination with k nearest neighbors (kNN) and support vector machine (SVM) classifiers[J].Optics &Laser Technology,2018,102:233-239.
[15]
Vance T,Reljin N,Lazarevic A,et al.The 2010 International Joint Conference on Neural Networks (IJCNN):Classification of LIBS protein spectra using support vector machines and adaptive local hyperplanes[C]// Barcelona:[s.n.],2010:1-7.
[16]
Varmuza K,Filzmoser P.Introduction to multivariate statistical analysis in chemometrics[M].CRC Press,2016.
[17]
Thompson J,Wiens R,Barefield J,et al.Remote laser-induced breakdown spectroscopy analyses of Dar al Gani 476 and Zagami Martian meteorites[J].Journal of Geophysical Research:Planets,2006,111(E5).
[18]
De Giacomo A,Dell'aglio M,De Pascale O,et al.Laser induced breakdown spectroscopy on meteorites[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2007,62(12):1606-1611.
[19]
Dell’aglio M,De Giacomo A,Gaudiuso R,et al.Laser induced breakdown spectroscopy applications to meteorites:Chemical analysis and composition profiles[J].Geochimica et Cosmochimica Acta,2010,74(24):7329-7339.
[20]
Colao F,Fantoni R,Lazic V,et al.Investigation of LIBS feasibility for in situ planetary exploration:an analysis on Martian rock analogues[J].Planetary and Space Science,2004,52(1-3):117-123.
[21]
Sallé B,Cremers D A,Maurice S,et al.Evaluation of a compact spectrograph for in-situ and stand-off laser-induced breakdown spectroscopy analyses of geological samples on Mars missions[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2005,60(6):805-815.
[22]
Sallé B,Lacour J-L,Mauchien P,et al.Comparative study of different methodologies for quantitative rock analysis by laser-induced breakdown spectroscopy in a simulated Martian atmosphere[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2006,61(3):301-313.
[23]
Derome D,Cathelineau M,Cuney M,et al.Mixing of sodic and calcic brines and uranium deposition at McArthur River,Saskatchewan,Canada:a Raman and laser-induced breakdown spectroscopic study of fluid inclusions[J].Economic Geology,2005,100(8):1529-1545.
[24]
Derome D,Cathelineau M,Fabre C,et al.Paleo-fluid composition determined from individual fluid inclusions by Raman and LIBS:application to mid-proterozoic evaporitic Na-Ca brines (Alligator Rivers Uranium Field,northern territories Australia)[J].Chemical Geology,2007,237(3-4):240-254.
[25]
Fabre C,Boiron M-C,Dubessy J,et al.Advances in lithium analysis in solids by means of laser-induced breakdown spectroscopy:an exploratory study[J].Geochimica et Cosmochimica Acta,2002,66(8):1401-1407.
[26]
Wisbrun R,Schechter I,Niessner R,et al.Detector for trace elemental analysis of solid environmental samples by laser plasma spectroscopy[J].Analytical Chemistry,1994,66(18):2964-2975.
[27]
Braga J W B,Trevizan L C,Nunes L C,et al.Comparison of univariate and multivariate calibration for the determination of micronutrients in pellets of plant materials by laser induced breakdown spectrometry[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2010,65(1):66-74.
[28]
Zaytsev S M,Popov A M,Chernykh E V,et al.Comparison of single-and multivariate calibration for determination of Si,Mn,Cr and Ni in high-alloyed stainless steels by laser-induced breakdown spectrometry[J].Journal of Analytical Atomic Spectrometry,2014,29(8):1417-1424.
[29]
Chollet F.Deep Learning with Python[M].Greenwich:Manning Publications Co.,2017:53-54.
[30]
Yaroshchyk P,Death D,Spencer S.Comparison of principal components regression,partial least squares regression,multi-block partial least squares regression,and serial partial least squares regression algorithms for the analysis of Fe in iron ore using LIBS[J].Journal of Analytical Atomic Spectrometry,2012,27(1):92-98.
[31]
Devangad P,Unnikrishnan V,Tamboli M,et al.Quantification of Mn in glass matrices using laser induced breakdown spectroscopy (LIBS) combined with chemometric approaches[J].Analytical Methods,2016,8(39):7177-7184.
[32]
Alfarraj B A,Sanghapi H K,Bhatt C R,et al.Qualitative analysis of dairy and powder milk using laser-induced breakdown spectroscopy (LIBS)[J].Applied Spectroscopy,2018,72(1):89-101.
[33]
Martin W,Wiese W,Musgrove A,et al.NIST atomic spectra database[J].Memorie Della Societa Astronomica Italiana Supplementi,2005,8(1):96.
