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−1, 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.     

Portable fiber-optic laser-induced breakdown spectroscopy system for the quantitative analysis of minor elements in steel

In this paper, we developed a portable laser-induced breakdown spectroscopy(LIBS) using an optical fiber to deliver laser energy and used it to quantitatively analyze minor elements in steel.The R~2 factors of calibration curves of elements Mn, Ti, V, and Cr in pig iron were 0.9965,0.9983, 0.9963, and 0.991, respectively, and their root mean square errors of cross-validation were 0.0501, 0.0054, 0.0205, and 0.0245 wt%, respectively. Six test samples were used for the validation of the performance of the calibration curves established by the portable LIBS. The average relative errors of elements Mn, Ti, V, and Cr were 2.5%, 11.7%, 13.0%, and 5.6%,respectively. These results were comparable with most results reported in traditional LIBS in steel or other matrices. However, the portable LIBS is flexible, compact, and robust, providing a promising prospect in industrial application.     

Evaluation of elemental status of ancient human bone samples from Northeastern Hungary dated to the 10th century AD by XRF

The present study is a multielemental analysis of bone samples belonging to skeletal individuals originating from two contemporaneous (10th century AD) cemeteries (Tiszavasvári Nagy-Gyepáros and Nagycserkesz-Nádasibokor sites) in Northeastern Hungary, using the XRF analytical technique. Emitted X-rays were detected in order to determine the elemental composition of bones and to appreciate the possible influence of the burial environment on the elemental content of the human skeletal remains. Lumbar vertebral bodies were used for analysis. Applying the ED(P)XRF technique concentration of the following elements were determined: P, Ca, K, Na, Mg, Al, Cl, Mn, Fe, Zn, Br and Sr. The results indicated post mortem mineral exchange between the burial environment (soil) and bones (e.g. the enhanced levels of Fe and Mn) and referred to diagenetic alteration processes during burials. However, other elements such as Zn, Sr and Br seemed to be accumulated during the past life. On the basis of statistical analysis, clear separation could not be observed between the two excavation sites in their bone elemental concentrations which denoted similar diagenetic influences, environmental conditions. The enhanced levels of Sr might be connected with the past dietary habits, especially consumption of plant food.     

EDXRF analysis of Marajoara pubic covers

This work evaluated the elemental composition of decorated pottery pubic covers (tangas) from the Marajoara culture of Marajó Island (at the mouth of the Amazon River, Brazil) using EDXRF technique. The XRF system used in this work consists in a Si(Li) detector from ORTEC, with resolution of 180 eV, at 5.9 keV, and a mini X-ray tube with Mo anode. The elements identified in the samples were: S, Cl, K, Ca, Ti, Mn, Fe, Cu, Zn, Ga, Rb, Sr, Y, Zr and Pb. Principal components analysis (PCA) was used to evaluated the provenance of the samples.     

Characterization of the Delamination Defects in Marine Steel Using Laser-Induced Breakdown Spectroscopy

In this paper,two types of comparison analyses,bulk analysis and defect analysis,were carried out for marine steel.The results of laser-induced breakdown spectroscopy(LIBS)were compared with those of spark optical emission spectrometry(Spark-OES) and scanning electron microscopy/energy dispersion spectroscopy(SEM/EDS) in the bulk and defect analyses.The comparison of the bulk analyses shows that the chemical contents of C,Si,Mn,P,S and Cr obtained from LIBS agree well with those determined using Spark-OES.The LIBS is slightly less precise than Spark-OES.Defects were characterized in the two-dimensional distribution analysis mode for Al,Mg,Ca,Si and other elements.Both the LIBS and SEM/EDS results show the enrichment of Al,Mg,Ca and Si at the defect position and the two methods agree well with each other.SEM/EDS cannot provide information about the difference in the chemical constituents when the differences between the defect position and the normal position are not significant.However,LIBS can provide this information,meaning that the sensitivity of LIBS is higher than that of SEM/EDS.LIBS can be used to rapidly characterize marine steel defects and provide guidance for improving metallurgical processes.     

X-ray microfluorescence analysis of pigments in decorative paintings from the sarcophagus cartonnage of an Egyptian mummy

This work characterized the elemental composition of the pigments used in decorative paintings from the sarcophagus cartonnage fragments of an Egyptian mummy, using μXRF with Synchrotron Radiation. This female mummy (n.158) is considered one of the most important pieces of the National Museum (Rio de Janeiro, Brazil) because of its unconventional embalming with legs and arms swathed separately. The measurements were performed at the XRF beamline D09B of the Brazilian Synchrotron Light Laboratory (LNLS), using white beam and a Si(Li) detector with resolution of 165 eV at 5.9 keV. The elements found in the samples were: Si, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Sr, Hg and Pb.     

Quantitative analysis of saindha salt using laser induced breakdown spectroscopy and cross-validation with ICP-MS

Saindha salt is considered to be more advantageous than the other edible salts for the patients suffering from diabetes,blood pressure and kidney diseases.To explore the constituent elements of this salt,laser induced breakdown spectroscopy(LIBS) has been exploited for its qualitative and quantitative analysis.The third harmonic(355 nm) of a Q-switched Nd:YAG laser has been used to produce the saindha salt plasma and the time integrated optical emission spectra were registered using a set of six miniature spectrometers covering the spectral range of 230-805 nm.The spectroscopic analysis of the emission spectra predominately revealed numerous neutral or singly ionized emission lines of Ca,Mg,Na,K,Fe,Sr,Si,Li and Al.The laser produced plasma was characterized by calculating the electron temperature from the Boltzmann plots and the electron number density from the Stark broadened line profile as a function of laser irradiance and distance from the target sample.The relative concentration of the constituent elements was extracted by the integrated line intensities of the strongest spectral line of each element using the self-calibration-LIBS(SC-LIBS) and one-line calibration free-LIBS(OLCF-LIBS) methods.For cross-validation,the LIBS results have been compared with that obtained from the inductively coupled plasma-mass spectroscopy(ICP-MS) showing good agreement.     

Fast identification of mural pigments at Mogao Grottoes using a LIBS-based spectral matching algorithm

To quickly identify the mineral pigments in the Dunhuang murals, a spectral matching algorithm (SMA) based on four methods was combined with laser-induced breakdown spectroscopy (LIBS) for the first time. The optimal range of LIBS spectrum for mineral pigments was determined using the similarity value between two different types of samples of the same pigment. A mineral pigment LIBS database was established by comparing the spectral similarities of tablets and simulated samples, and this database was successfully used to identify unknown pigments on tablet, simulated, and real mural debris samples. The results show that the SMA method coupled with the LIBS technique has great potential for identifying mineral pigments.     

酵母菌吸附锶离子后沉淀物的减量化处理

为了探讨酵母菌吸附Sr~(2+)后沉淀物的处理及Sr~(2+)浓缩条件,在不同焚烧温度和不同焚烧时间下对絮凝后的样品进行焚烧处理,同时对焚烧产物进行了X射线衍射(XRD)、X射线荧光光谱(XRF)、扫描电镜-能谱(SEM-EDS)、热重(TG-DTG)分析;并对焚烧产物中的Sr~(2+)进行了进一步的酸浸提取、浓缩。研究结果显示:焚烧温度1 200℃,焚烧时间1.0h,样品减容率和减量率分别为92.9%和91.0%;生成了较为稳定的Al2O3、AlPO_4、Sr_5Al_2O_8等主要物质;TG-DTG分析显示样品热解温度主要集中在800℃以下,质量损失约达90.0%;在硝酸浓度为3 mol/L、固液比为1∶75、浸取时间为60 min的条件下,Sr~(2+)的浸取率为98.1%,浓缩率为86.1%。     

Line identification of extreme ultraviolet(EUV) spectra from low-Z impurity ions in EAST tokamak plasmas

Extreme ultraviolet(EUV) spectra emitted from low-Z impurity ions in the wavelength range of10–500 ? were observed in Experimental Advanced Superconducting Tokamak(EAST)discharges. Several spectral lines from K-and L-shell partially ionized ions were successfully observed with sufficient spectral intensities and resolutions for helium, lithium, boron, carbon,oxygen, neon, silicon and argon using two fast-time-response EUV spectrometers of which the spectral intensities are absolutely calibrated based on the intensity comparison method between visible and EUV bremsstrahlung continua. The wavelength is carefully calibrated using wellknown spectra. The lithium, boron and silicon are individually introduced for the wall coating of the EAST vacuum vessel to suppress mainly the hydrogen and oxygen influxes from the vacuum wall, while the carbon and oxygen intrinsically exist in the plasma. The helium is frequently used as the working gas as well as the deuterium. The neon and argon are also often used for the radiation cooling of edge plasma to reduce the heat flux onto the divertor plate. The measured spectra were analyzed mainly based on the database of National Institute of Standards and Technology. As a result, spectral lines of He Ⅱ, Li Ⅱ–Ⅲ, B Ⅳ–Ⅴ, C Ⅲ–Ⅵ, O Ⅲ–Ⅷ, Ne Ⅱ–Ⅹ,Si Ⅴ–Ⅻ, and Ar Ⅹ–XVI are identified in EAST plasmas of which the central electron temperature and chord-averaged electron density range in T_(e0)=0.6–2.8 keV and n_e=(0.5–6.0)×10~(19) m~(-3), respectively. The wavelengths and transitions of EUV lines identified here are summarized and listed in a table for each impurity species as the database for EUV spectroscopy using fusion plasmas.     

Analytical study of seashell using laser-induced breakdown spectroscopy

Seashell has been applied as an indicator for ocean research and element analysis of the seashell is used to track biological or environmental evolution.In this work,laser-induced breakdown spectroscopy(LIBS) was applied for elementary analysis of an ezo scallop-shell,and a graphite enrichment method was used as the assistance.It was found that LIBS signal intensity of Ca fluctuated less than 5%,in spite of the sampling positions,and Sr/Ca was related to the shell growth.A similar variation was also found when using a direct LIBS analysis on the shell surface,and it might be more practicable to track shell growth by investigating Sr/Ca ratio with Sr ionic line at 421.6 nm.The obtained results prove that calcium(Ca) is qualified as an internal reference for shell analysis,and LIBS is a potential analytical method for seashell study.     

Improvement in classification accuracy of stainless steel alloys by laser-induced breakdown spectroscopy based on elemental intensity ratio analysis

Laser-induced breakdown spectroscopy(LIBS) is a useful technique for accurate sorting of metal scrap by chemical composition analysis.In this work,a method for intensity-ratiobased LIBS classification of stainless steel applicable to highly fluctuating LIBS signal conditions is proposed.The spectral line pairs for intensity ratio calculation are selected according to elemental concentration and upper levels of emission lines.It is demonstrated that the classification accuracy can be significantly improved from that of full-spectra principal component analysis or intensity-based analysis.The proposed method is considered to be suited to an industrial scrap sorting system that requires minimal maintenance and low system price.     

A Hydrogel's Formation Device for Quick Analysis of Liquid Samples Using Laser-Induced Breakdown Spectroscopy

The laser-induced breakdown spectroscopy technique has irreplaceable advantages in the field of detection due to its multi-phase specimen detection ability.The development of the LIBS technique for liquid analysis is obstructed by its inherent drawbacks like the surface ripples and extinction of emitted intensity,which make it unpractical.In this work,an in-situ hydrogel formation sampling device was designed and used the hydrogel as the detection phase of LIBS for Cu,Cr and Al in an aqueous solution.With the measured amount of resin placed in the device,the formed hydrogel could be obtained within 20 s after putting the device into water solution.The formed hydrogel could be directly analyzed by LIBS and reflect the elemental information of the water sample.The prominent performance made this hydrogel's formation device especially suitable for quick in-situ environmental liquid analysis using LIBS.     

脱氮硫杆菌的筛选及其对锶离子的矿化作用

放射性污染日益严重,其中锶污染作为土壤典型污染之一成为研究热点。土壤中存在着一些矿化菌,能够对锶离子进行矿化固定。本实验对从土壤中分离的3株脱氮硫杆菌的特性及其对Sr~(2+)的矿化行为进行了研究,发现该菌对1.0g/L模拟Sr~(2+)污染的去除率可达80%。扫描电子显微镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)等结果显示,矿化产物为硫酸锶。可见,利用脱氮硫杆菌治理土壤中Sr~(2+)污染具有可行性,该方法将会有一定应用前景。     

Effect of parameter setting and spectral normalization approach on study of matrix effect by laser induced breakdown spectroscopy of Ag–Zn binary composites

The complex nature of laser-material interaction causes non-stoichiometric ablation of alloy samples.This is attributed to matrix effect, which reduces analyzing capability. To address this issue, the analytical performance of three different normalization methods, namely normalization with background, internal normalization and three point smoothing techniques at different parameter settings is studied for quantification of Ag and Zn by Laser induced breakdown spectroscopy(LIBS).The LIBS spectra of five known concentration of silver zinc binary composites have been investigated at various laser irradiances(LIs). Calibration curves for both Ag(I) line(4d~(10)5s~2S_(1/2)→4d~(10)5p~2P_(1/2) at 338.28 nm) and Zn(I) line(4s5s~3S_1→4s4p~3P_2 at 481.053 nm) have been determined at LI of 5.86?×?10~(10)W cm~(-2). Slopes of these calibration curves provide the valuation of matrix effect in the Ag–Zn composites. With careful sample preparation and normalization after smoothing at optimum parameter setting(OPS), the minimization of sample matrix effect has been successfully achieved. A good linearity has been obtained in Ag and Zn calibration curve at OPS when normalized the whole area of spectrum after smoothing and the obtained coefficients of determination values were R~2?=?0.995 and 0.998 closer to 1. The results of matrix effect have been further verified by analysis of plasma parameters. Both plasma parameters showed no change with varying concentration at OPS. However, at high concentration of Ag, the observed significant changes in both plasma parameters at common parameter setting PS-1 and PS-2 were the gesture of matrix effect. In our case, the better analytical results were obtained at smoothing function with optimized parameter setting that indicates it is more efficient than normalization with background and internal normalization method.     

古代青金石颜料的质子激发X荧光分析

用质子激发Ｘ荧光分析（ＰＩＸＥ）方法分析了敦煌莫高窟、麦积山石窟、炳灵寺石窟的１１个朝代壁画中所使用的青金石颜料，获得了该颜料的定性定量分析结果．通过对１８个样品的分析对比，对青金石颜料中所含的Ｍｎ、Ｃｒ、Ａｓ、Ｔｉ、Ｓｒ、Ｓｂ、Ｚｎ等微量元素作了讨论，并与Ｘ射线荧光（ＸＲＦ）、Ｘ射线衍射（ＸＲＤ）、电子探针分析结果作了对比．     

Influence of target temperature on femtosecond laser-ablated brass plasma spectroscopy

Spectral intensity,electron temperature and density of laser-induced plasma(LIP) are important parameters for affecting sensitivity of laser-induced breakdown spectroscopy(LIBS).Increasing target temperature is an easy and feasible method to improve the sensitivity.In this paper,a brass target in a temperature range from 25℃ to 200℃ was ablated to generate the LIP using femtosecond pulse.Time-resolved spectral emission of the femtosecond LIBS was measured under different target temperatures.The results showed that,compared with the experimental condition of 25℃,the spectral intensity of the femtosecond LIP was enhanced with more temperature target.In addition,the electron temperature and density were calculated by Boltzmann equation and Stark broadening,indicating that the changes in the electron temperature and density of femtosecond LIP with the increase of the target temperature were different from each other.By increasing the target temperature,the electron temperature increased while the electron density decreased.Therefore,in femtosecond LIBS,a hightemperature and low-density plasma with high emission can be generated by increasing the target temperature.The increase in the target temperature can improve the resolution and sensitivity of femtosecond LIBS.     

头发中钙及微量元素含量的性别差异研究

用X射线荧光分析法测定了上海和苏州地区4127例居民头发中钙及9种微量元素的含量,发现不管地区与年龄如何,发中Sr、Mn、Ca的含量总是女性高于男性,而Pb含量总是男性高于女性,差异非常显著(p<0.01)。从不同生理条件下发中元素含量的比较中也可以看出,这些元素必然与女性的某些特殊生理功能有联系。     

Temporal and spatial evolution measurement of laser-induced breakdown spectroscopy on hydrogen retention in tantalum

Fuel retention measurement on plasma-facing components is an active field of study in magnetic confinement nuclear fusion devices.The laser-induced breakdown spectroscopy(LIBS)diagnostic method has been well demonstrated to detect the elemental distribution in PFCs.In this work,an upgraded co-axis LIBS system based on a linear fiber bundle collection system has been developed to measure the hydrogen(H) retention on a tantalum(Ta) sample under a vacuum condition.The spatial resolution measurement of the different positions of the LIBS plasma can be achieved simultaneously with varying delay times.The temporal and spatial evolution results of LIBS plasma emission show that the H plasma observably expands from the delay times of 0-200 ns.The diameter of Ta plasma is about 6 mm which is much less than the size of H plasma after 200 ns.The difference in the temporal and spatial evolution behaviors between H plasma and Ta plasma is due to the great difference in the atomic mass of H and Ta.The depth profile result shows that H retention mainly exists on the surface of the sample.The temporal and spatial evolution behaviors of the electron excited temperature are consistent with that of the Ta emission.The result will further improve the understanding of the evolution of the dynamics of LIBS plasma and optimize the current collection system of in situ LIBS in fusion devices.     

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.