Matrix effect suppressing in the element analysis of soils by laser-induced breakdown spectroscopy with acoustic correction

Laser-induced breakdown spectroscopy(LIBS)has been used for soil analysis,but its measurement accuracy is often influenced by matrix effects of different kinds of soils.In this work,a method for matrix effect suppressing was developed using laser-induced plasma acoustic signals to correct the original spectrum,thereby improving the analysis accuracy of the soil elements.A good linear relationship was investigated firstly between the original spectral intensity and the acoustic signals.The relative standard deviations(RSDs)of Mg,Ca,Sr,and Ba elements were then calculated for both the original spectrum and the spectrum with the acoustic correction,and the RSDs were significantly reduced with the acoustic correction.Finally,calibration curves of MgⅠ285.213 nm,CaⅠ422.673 nm,SrⅠ460.733 nm and BaⅡ455.403 nm were established to assess the analytical performance of the proposed acoustic correction method.The values of the determination coefficient(R~2)of the calibration curves for Mg,Ca,Sr,and Ba elements,corrected by the acoustic amplitude,are improved from 0.9845,0.9588,0.6165,and 0.6490 to 0.9876,0.9677,0.8768,and 0.8209,respectively.The values of R~2 of the calibration curves corrected by the acoustic energy are further improved to 0.9917,0.9827,0.8835,and 0.8694,respectively.These results suggest that the matrix effect of LIBS on soils can be clearly improved by using acoustic correction,and acoustic energy correction works more efficiently than acoustic amplitude correction.This work provides a simple and efficient method for correcting matrix effects in the element analysis of soils by acoustic signals.

Elemental and proximate analysis of coal by x-ray fluorescence assisted laser-induced breakdown spectroscopy

Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in thermal power plants,the measurement repeatability of LIBS needs to be further improved due to the difficulty in controlling the stability of the generated plasmas at present.In this paper,we propose a novel x-ray fluorescence(XRF) assisted LIBS method for high repeatability analysis of coal quality,which not only inherits the ability of LIBS to directly analyze organic elements such as C and H in coal,but also uses XRF to make up for the lack of stability of LIBS in determining other inorganic ash-forming elements.With the combination of elemental lines in LIBS and XRF spectra,the principal component analysis and the partial least squares are used to establish the prediction model and perform multi-elemental and proximate analysis of coal.Quantitative analysis results show that the relative standard deviation(RSD) of C is 0.15%,the RSDs of other elements are less than 4%,and the standard deviations of calorific value,ash content,sulfur content and volatile matter are 0.11 MJ kg,0.17%,0.79% and 0.41%respectively,indicating that the method has good repeatability in determination of coal quality.This work is helpful to accelerate the development of LIBS in the field of rapid measurement of coal entering the power plant and on-line monitoring of coal entering the furnace.

Quantitative analysis of steel and iron by laser-induced breakdown spectroscopy using GA-KELM

According to the multiple researches in the last couple of years, laser-induced breakdown spectroscopy(LIBS) has shown a great potential for rapid analysis in steel industry.Nevertheless, the accuracy and precision may be limited by complex matrix effect and selfabsorption effect of LIBS seriously. A novel multivariate calibration method based on genetic algorithm-kernel extreme learning machine(GA-KELM) is proposed for quantitative analysis of multiple elements(Si, Mn, Cr, Ni, V, Ti, Cu, Mo) in forty-seven certified steel and iron samples.First, the standardized peak intensities of selected spectra lines are used as the input of model.Then, the genetic algorithm is adopted to optimize the model parameters due to its obvious capability in finding the global optimum solution. Based on these two steps above, the kernel method is introduced to create kernel matrix which is used to replace the hidden layer's output matrix. Finally, the least square is applied to calculate the model's output weight. In order to verify the predictive capability of the GA-KELM model, the R-square factor(R^2), Root-meansquare Errors of Calibration(RMSEC), Root-mean-square Errors of Prediction(RMSEP) of GAKELM model are compared with the traditional PLS algorithm, respectively. The results confirm that GA-KELM can reduce the interference from matrix effect and self-absorption effect and is suitable for multi-elements calibration of LIBS.

Relative spectral response calibration using Ti plasma lines

This work introduces the branching ratio(BR) method for determining relative spectral responses,which are needed routinely in laser induced breakdown spectroscopy(LIBS). Neutral and singly ionized Ti lines in the 250–498 nm spectral range are investigated by measuring laser-induced micro plasma near a Ti plate and used to calculate the relative spectral response of an entire LIBS detection system. The results are compared with those of the conventional relative spectral response calibration method using a tungsten halogen lamp, and certain lines available for the BR method are selected. The study supports the common manner of using BRs to calibrate the detection system in LIBS setups.

In situ Analysis of Na and K in a Laminar Premixed Flame by Laser-induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy（LIBS） was used to in situ monitor the concentration of alkali elements in combustion environments. Particular efforts were made to optimize the temporally resolved spectra of Na and K elements. Calibration curves were constructed by relating the intensities of the specific lines to the corres- ponding elemental concentrations. The detection limits of Na and K elements were found to be temperature- dependent. The results indicate that LIBS can be a powerful tool for in situ monitoring Na and K concentrations in combustion environments.

Quantitative Analysis of Fe Content in Iron Ore via External Calibration in Conjunction with Internal Standardization Method Coupled with LIBS

The external calibration in conjunction with internal standardization（ECIS） coupled with laser-induced breakdown spectroscopic（LIBS） technique was proposed to perform the quantitative analysis of Fe content in iron ore The plasma temperature and the electron number density were calculated to prove that the plasma was under local thermodynamic equilibrium（LTE） conditions and to ensure that the integral intensities of Fe I lines were reasonable. In addition, the result of the quantitative analysis shows a content of （20.26±0.59）% by mass of Fe in the iron ore. It was determined by four calibration curves, drawn for four emission lines of Fe I（373.48, 373.71,404.58 and 438.35 nm） normalized by Mn I line, base on the ECIS method which can eliminate the influence of matrix effect and improve the accuracy of quantitative analysis, compared with the standard addition method. Both the results of these two analytical methods were compared with that listed in the Standard Substance Certificate. The percentage content of Fe in the same sample of iron ore by the ECIS method was （20.17±0.08）% by mass, which shows a good performance to analyze the Fe content of iron ore in combination with LIBS.

Recent progress on the application of LIBS for metallurgical online analysis in China

Recent progress on the application of laser-induced breakdown spectroscopy （LIBS） for metallurgical analysis particularly achieved by Chinese research community is briefly reviewed in this article. The content is mainly focused on the progress in experimental research and calibration methods toward LIBS applications for metallurgical online analysis over the past few years. Different experiment setups such as single-pulse and double-pulses LIBS schematics are introduced. Various calibration methods for different metallic samples are presented. Quantitative results reported in the literature and obtained in the analysis of various samples with different calibration methods are summarized. At the last section of this article, the difficulties of LIBS application for molten metal analysis in a furnace are discussed.

Review of methodological and experimental LIBStechniques for coal analysis and their application in power plants in China

Laser-induced breakdown spectroscopy (LIBS) is an emerging analytical spectroscopy technique. This review presents the main recent developments in China regarding the implementation of LIBS for coal analysis. The paper mainly focuses on the progress of the past few years in the fundamentals, data pretreatment, calibration model, and experimental issues of LIBS and its application to coal analysis. Many important domestic studies focusing on coal quality analysis have been conducted. For example, a proposed novel hybrid quantification model can provide more reproducible quantitative analytical results; the model obtained the average absolute errors (AREs) of 0.42%, 0.05%, 0.07%, and 0.17% for carbon, hydrogen, volatiles, and ash, respectively, and a heat value of 0.07 MJ/kg. Atomic/ionic emission lines and molecular bands, such as CN and C-2, have been employed to generate more accurate analysis results, achieving an ARE of 0.26% and a 0.16% limit of detection (LOD) for the prediction of unburned carbon in fly ashes. Both laboratory and on-line LIBS apparatuses have been developed for field application in coal-fired power plants. We consider that both the accuracy and the repeatability of the elemental and proximate analysis of coal have increased significantly and further efforts will be devoted to realizing large-scale commercialization of coal quality analyzer in China.