Multi-element analysis of iron ore pellets by Laser-induced Breakdown Spectroscopy and Principal Components Regression

Laser-induced Breakdown Spectroscopy (LIBS) in combination with Principal Components Regression (PCR) has been applied to determine the elemental composition of a series of run-of-mine (ROM) iron ore samples. The samples were presented for measurement both as compressed pellets and as loose chipped material. The present paper details the results of the measurements of the compressed pellets. Results from ore chips will be reported separately. LIBS spectral data was recorded in three separate spectral regions to measure major, minor and trace components of the iron ore sample pellets. Background stripping, normalization and spectral cleaning were applied to minimize the relative standard deviations of the LIBS data. PCR analysis was then applied to produce calibration models for iron, aluminum, silicon, manganese, potassium and phosphorous. These calibration models were then validated using independent LIBS measurements. Robust calibration models were determined for iron, aluminum, silicon and potassium, whilst the results for manganese were encouraging. Phosphorous, present at low levels in the ores measured, remained the most difficult element to determine accurately. The combination of LIBS and PCR shows potential for in-situ on-line determination of ore composition.     

激光诱导击穿光谱法对钢中夹杂物类型的表征

激光诱导击穿光谱( LIBS)不仅可以对材料整体成分进行分析,还可进行微区及成分分布分析。本实验采用激光诱导击穿光谱对两牌号钢铁样品进行扫描分析,尝试对34CrNiMo6钢中的MnS夹杂物和重轨钢中的Si-Al-Ca-Mg复合夹杂物进行表征。结果表明,34CrNiMo6钢中元素信号的二维强度分布及元素通道合成后,个别位置Mn及S两元素的信号强度同时异常高,可确定试样中存在较多MnS夹杂物;重轨钢中元素的二维强度分布及元素通道合成后,个别位置Si、Ca、Mg及Al元素的信号同时异常高,可确定试样中存在Si-Al-Ca-Mg复合夹杂物。采用扫描电子显微镜/能谱法( SEM/EDS)对上述样品中夹杂物的对比分析结果表明,两种方法对夹杂物类型的判定结果一致。     

激光诱导击穿光谱法分析焊丝样品

采用激光诱导击穿光谱法(LIBS)对焊丝样品中的硅、锰、磷、硫、铬及镍元素进行测定。采用扫描电子显微镜和激光共聚焦显微镜观察了样品经激光脉冲烧蚀后的形貌,并考察了各元素的谱线强度与激光脉冲个数之间的关系,从而确定了预剥蚀激光脉冲个数。通过分析标准样品建立了单个元素的谱线强度与其质量分数之间的标准曲线,相关系数在0.989~0.999之间。本方法对焊丝样品的分析结果与经典的电感耦合等离子体原子发射光谱法和高频红外硫碳分析方法的测定结果相吻合,其精密度稍差于经典的分析方法。     

Phosphate ore beneficiation via determination of phosphorus-to-silica ratios by Laser Induced Breakdown Spectroscopy

We report development and application of an in-situ applicable method to determine phosphate ore rock quality based on Laser-Induced Breakdown Spectroscopy (LIBS). This is an economically viable method for real-time evaluation of ore phosphate rocks in order to separate high-silica pebbles prior to deep beneficiation. This is achieved by monitoring relative emission line intensities from key probe elements via single laser ablation shots: the ratio of the phosphorous to silica line intensities (P/Si ratio) provides a simple and reliable indicator of ore rock quality. This is a unique LIBS application where no other current analytical spectroscopic method (ICP or XRF) can be applied. Method development is discussed, and results with actual ore samples are presented.     

高分辨激光诱导击穿光谱技术用于碳质页岩光谱特征分析

碳质页岩是一种重要的非常规油气源岩,包含丰富的页岩气储存信息。在地质油气勘探领域,识别物性相近的碳质页岩是地质学的难题之一。为快速准确判别碳质页岩特性,本研究利用激光诱导击穿光谱( LIBS)技术对碳质页岩的光谱进行特征分析。以1064 nm纳秒脉冲激光作为激发光源,采用高分辨中阶梯光栅光谱仪配合ICCD搭建高分辨光学系统,利用LIBS装置分析四川盆地某井2396~3428 m不同深度处的5个典型碳质页岩样品,共获取碳质页岩中主量元素Si,Al,Fe,Ca,Mg,K和微量元素Cu,Cr,Ni,Sr,Mn,Ti,Rb等22种元素的350条发射谱线。基于高分辨LIBS系统采集的丰富谱线信息,采用主成分分析( PCA)法提取光谱贡献率最大的主成分得分二维图,识别不同类别碳质页岩样品,实现定性分析。结果表明,高分辨LIBS实验装置不仅可用于碳质页岩主量元素Si,Al,Fe,Ca,Mg,K等谱线分析,同时对微量元素如Ni,Cr,Mn,Sr等也具有很好的灵敏性。此外,LIBS技术与主成分分析( PCA)法结合可以更好地用于碳质页岩定性分析领域,提供科学的碳质页岩岩性判断数据和快速的分类手段,为页岩气开采和评估提供强有力的工具。     

Determination of Lead and Copper in Ligusticum wallichii by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy was used for the analysis of the Chinese traditional medicine, Ligusticum wallichii. The laser energy and delay time were optimized to obtain best spectral quality. The limits of detection for lead and copper were 15.7 and 6.3?µg?g^?1, respectively. Multiple linear regression models between the laser-induced breakdown spectroscopy intensity and the mass fraction of lead and copper were constructed. Good agreement was observed between the actual concentrations and predicted values obtained by the models. These results demonstrate that the laser-induced breakdown spectroscopy coupled with multiple linear regression is suitable for the determination of heavy metals in Chinese traditional medicine.     

Quantitative Analysis of Metallic Elements in Tobacco and Tobacco Ash by Calibration Free Laser-Induced Breakdown Spectroscopy

Cigarette smoking may be a substantial source of intake of some hazardous elements to the human health. In this work calibration-free laser-induced breakdown spectroscopy technique was employed to investigate the trace metallic elements (Fe, Ca, Al, Cu, K, Li, Mg, Mn, Na, Sr, Ti, and Zn) concentration in tobacco and tobacco ash. Moreover, variation of metallic elements mass concentration between tobacco and tobacco ash has been observed.     

Examination of Polish Identity Documents by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was applied to the preliminary examination of Polish documents – passports and identity cards – for forensic purposes. Several security features of potentially high discrimination capability were selected at both the passports (Alphagram, serial number, the contour map of Europe, and emblem) and identity cards (kinegram, the date of birth, and emblem). Different elemental compositions were identified after comparing the spectra recorded from various measurement locations. It was possible to identify characteristic atomic emission from several elements (such as Ti, Ca, K, Fe, Cr, Mg, Na, La, Cd, Li, V, Al, Mn, Ni, and Cu) based on the type of document, issue date, and evaluated area. In the case of passports, the potentially good discriminators with unique elemental composition were identified, e.g., the serial number and the contour map of Europe printed with the use of intaglio printing technique. Identity cards with the cover of polycarbonate foil constitute a very difficult sample to analyze because of the foil’s influence on the laser ablation phenomenon. This study presents the potential of LIBS as an effective and useful technique to analyze Polish passports for forensic purposes. Its many advantages provide a good alternative to the analytical methods routinely used for the examination of these objects.     

Quantitative Analysis of Roman Archeological Ceramics by Laser-Induced Breakdown Spectroscopy

In recent decades, numerous analytical techniques have been used for the analysis of archeological samples. Laser-induced breakdown spectroscopy (LIBS) is a promising technique due to its practically nondestructive nature and minimal sample preparation. In this work, LIBS was used for the qualitative and quantitative elemental analyses of pottery manufactured in ancient settlements of Rome. The qualitative study showed that the ceramics were composed of Fe, Ca, and Mg. For quantitative analysis, calibration curves of Fe, Ca, and Mg were constructed with reference samples of each element in a KBr matrix with zinc as an internal standard. The results obtained by LIBS were compared with values obtained by atomic absorption.     

Progress in Research and Application of Micro-Laser-Induced Breakdown Spectroscopy

The technique of micro-laser-induced breakdown spectroscopy (μLIBS) usually refers to analyzing the surface of the sample using a compact focused laser beam in the optical microscope range. Compared to conventional laser-induced breakdown spectroscopy (LIBS), it can provide more abundant form, structure, and content information on a smaller, less sample condition. Hence, the application field is very wide. In this paper, the basic status of μLIBS in the selection of laser source and the structure of optical path system is introduced, and its application in metal, semiconductor, animal and plant fields is reviewed. The existing problems and potential development direction is pointed out.     

基于遗传算法和偏最小二乘法的土壤激光诱导击穿光谱定量分析研究

在空气环境下,采用激光诱导击穿光谱(LIBS)技术对土壤成分进行检测,建立了基于遗传算法(GA)和偏最小二乘法(PLS)的定量分析模型。将配制的58个土壤样品分为定标集、监控集和预测集,对11种组分Mn,Cr,Cu,Pb,Ba,Al2O3,Ca O,Fe2O3,Mg O,Na2O和K2O的含量分别进行预测。结果表明,GA作为一种谱线选择的预处理方法,可以有效减少用于PLS建模的光谱谱线的数目,从而简化模型。对于土壤中的大部分组成成分,GA-PLS模型能够显著改善传统PLS模型的预测能力。以Mn元素为例,浓度预测均方根误差(RMSEP)从0.0215%降低至0.0167%,平均百分比误差(MPE)从8.10%降低至5.20%。本研究为进一步提高土壤的LIBS定量分析准确度提供了方法参考。     

激光诱导击穿光谱(LIBS)结合机器学习算法快速测定石油焦中微量元素

石油焦中微量元素对其作为预焙阳极的性能起着决定性的作用。首先,通过基于LIBS光谱构建用于石油焦中铁(Fe)和铜(Cu)定量分析的PLS校正模型。然后,考察了不同光谱预处理(归一化、多元散射校正、标准正态变换、一阶导数和二阶导数)以及变量选择算法(粒子群优化算法和变量重要性投影)对PLS校正模型预测性能的影响。建立了一种基于激光诱导击穿光谱(Laser-induced breakdown spectroscopy, LIBS)结合偏最小二乘(Partial least squares, PLS)的石油焦中微量元素定量分析方法。结果显示,与其他PLS校正模型相比,基于二阶导数和变量重要性投影的PLS模型对Fe的预测性能最优,最优的交叉验证相关系数(R-squared cross validation,R²cv)为0.966 7,均方根误差(Root mean squared error cross validation, RMSEcv)为10.282 1 mg/kg,预测集的相关系数(R-squared prediction,R²p)为0.86...     

激光诱导荧光辅助激光诱导击穿光谱检测有源发光玻璃中的微量元素

在有源发光玻璃的制备过程中,通常需要掺杂微量元素,用于改善玻璃的发光性能,因此在生产过程中进行快速检测非常重要.本实验针对激光诱导击穿光谱技术(LIBS)分析玻璃中微量元素灵敏度不足的问题,利用激光诱导荧光辅助激光诱导击穿光谱技术(LIBS-LIF)检测了玻璃中3种微量元素Yb,Al和P.使用波长可调谐激光激发等离子体中的Yb+离子、Al原子和P原子,并对这3种粒子在激光诱导荧光中的跃迁过程进行了分析.结果表明,通过激光诱导荧光辅助激光诱导击穿光谱技术,Yb+离子、Al原子和P原子的光谱强度分别增强了23,50和8倍,大幅度提高了LIBS分析的灵敏度.     

飞秒-纳秒双脉冲激光诱导击穿光谱(LIBS)技术对合金的定量分析

激光诱导击穿光谱(Laser-induced breakdown spectroscopy, LIBS)技术几乎不受聚变环境中的强磁场影响,是一种最有希望实现托卡马克装置中面向等离子体材料(Plasma facing materials, PFMs)原位在线诊断的技术,已被用于多个托卡马克PFMs壁诊断。然而,LIBS技术对PFMs表面元素的探测限、定量分析以及PFMs的服役状态判定依旧面临很大挑战。采用同轴飞秒-纳秒激光协同技术,建立了飞秒-纳秒双脉冲激光诱导击穿光谱(fs-ns-DP-LIBS)技术,通过高峰值功率、低激光能量的飞秒激光诱导等离子体,再用纳秒激光增强常规单脉冲LIBS技术信号发射强度,进而提升常规单脉冲LIBS的探测灵敏度,同时结合6种合金标准样品,采用fs-ns-DP-LIBS技术对样品中的主要元素进行了定量分析,并进一步结合机器学习方法对6种合金进行种类判别。结果显示：在纳秒单脉冲和飞秒单脉冲LIBS检测中,Ni、Fe和Mo在400～800 nm波段没有观察到明显特征峰,仅观察到Cr的特征峰;在飞秒-纳秒脉冲间2μs延时,NiⅠ498.02 nm、FeⅠ517....     

Electrolyte Analysis in Blood Serum by Laser-Induced Breakdown Spectroscopy Using a Portable Laser

The fast and reliable analysis of electrolytes such as K, Na, Ca in human blood serum has become an indispensable tool for diagnosing and preventing diseases. Laser-induced breakdown spectroscopy (LIBS) has been demonstrated as a powerful analytical technique on elements. To apply LIBS to the quantitative analysis of electrolyte elements in real time, a self-developed portable laser was used to measure blood serum samples supported by glass slides and filter paper in this work. The partial least squares regression (PLSR) method was employed for predicting the concentrations of K, Na, Ca from serum LIBS spectra. Great prediction accuracies with excellent linearity were obtained for the serum samples, both on glass slides and filter paper. For blood serum on glass slides, the prediction accuracies for K, Na, Ca were 1.45%, 0.61% and 3.80%. Moreover, for blood serum on filter paper, the corresponding prediction accuracies were 7.47%, 1.56% and 0.52%. The results show that LIBS using a portable laser with the assistance of PLSR can be used for accurate quantitative analysis of elements in blood serum in real time. This work reveals that the handheld LIBS instruments will be an excellent tool for real-time clinical practice.     

Laser-induced breakdown spectroscopy for quantitative spectrochemical analysis of geological materials: effects of the matrix and simultaneous determination

A microscopic laser-induced breakdown spectrometer was used to evaluate the analytical matrix effect commonly observed in the analysis of geological materials. Samples were analyzed in either the powder or pressed pellet forms. Calibration curves of a number of iron and aluminum compounds showed a linear relationship between the elemental concentration and peak intensity. A direct determination of elemental content can thus be made from extrapolation on these calibration curves. To investigate matrix effects, synthetic model samples were prepared from various iron and aluminum compounds spiked with SiO₂ and CaCO₃. The addition of these matrices had a pronounced analytical effect on those compounds prepared as pressed pellets. However, results indicated the absence of matrix effects when the samples were presented to the laser as loose powders on tape and results were compared to certified values, indicating the reliability of this approach for accurate analysis, provided the sample particle diameters are greater than ≈100 μm. Finally, the simultaneous analysis of two different elements was demonstrated using powders on tape.     

激光诱导击穿光谱技术/多元二次非线性回归分析土壤中的铬元素

利用激光诱导击穿光谱(LIBS)技术对土壤中铬元素的含量进行了定量分析研究.由于土壤成分复杂,光谱谱线存在较严重的重叠干扰,若采用一元回归方法分析常得不到理想结果.为了更充分有效地利用光谱中信息,以土壤中Cr Ⅰ 425.43 nm和Fe Ⅰ 425.07 nm谱线的积分强度为自变量,Cr元素浓度为因变量,建立交叉降维近似多元非线性回归、多元二次非线性回归和平方降维近似多元非线性回归模型.对比分析表明,当添加Cr和Fe元素特征谱线强度交叉项影响时,所建立的多元二次非线性回归模型效果最佳,预测浓度与实际参考浓度之间线性关系达到0.9943,预测4个验证样品的相对误差分别为3.57％,0.76％,7.66％和2.24％.     

激光诱导击穿光谱对U元素的定量分析

铀矿是核领域最重要的矿产资源之一,快速、有效勘探铀矿资源能促进核领域平稳、健康发展。激光诱导击穿光谱(LIBS)技术具备多目标元素现场快速检测的优点,能实现铀矿资源准确、快速的现场分析。本工作基于LIBS技术对铀矿中U元素进行了定量分析,对比了偏最小二乘(PLS)和随机森林(RF)两种机器学习算法的定量效果。结果显示,RF模型的定量线性相关系数为0.996,对三个验证集的相对误差分别是22.33%、12.79%和12.04%;PLS模型的定量线性相关系数为0.997,对三个验证集的相对误差分别是4.33%、6.63%和6.85%。对比结果表明,本研究中的PLS模型定量准确度更高,同RF算法相比,PLS算法更适用于铀矿中U的LIBS定量分析。     

Analysis of Rock Varnish from the Mojave Desert by Handheld Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is a form of optical emission spectroscopy that can be used for the rapid analysis of geological materials in the field under ambient environmental conditions. We describe here the innovative use of handheld LIBS for the in situ analysis of rock varnish. This thinly laminated and compositionally complex veneer forms slowly over time on rock surfaces in dryland regions and is particularly abundant across the Mojave Desert climatic region of east-central California (USA). Following the depth profiling examination of a varnished clast from colluvial gravel in Death Valley in the laboratory, our in situ analysis of rock varnish and visually similar coatings on rock surfaces was undertaken in the Owens and Deep Spring valleys in two contexts, element detection/identification and microchemical mapping. Emission peaks were recognized in the LIBS spectra for the nine elements most abundant in rock varnish—Mn, Fe, Si, Al, Na, Mg, K, Ca and Ba, as well as for H, Li, C, O, Ti, V, Sr and Rb. Focused follow-up laboratory and field studies will help understand rock varnish formation and its utility for weathering and chronological studies.     

Classification of Chinese Herbal Medicine by Laser-Induced Breakdown Spectroscopy with Principal Component Analysis and Artificial Neural Network

Chinese herbal medicine has attracted increasing attention because of the unique and significant efficacy in various diseases. In this paper, three types of Chinese herbal medicine, the roots of Angelica pubescens, Codonopsis pilosula, and Ligusticum wallichii with different places of origin or parts, are analyzed and identified using laser-induced breakdown spectroscopy (LIBS) combined with principal component analysis (PCA) and artificial neural network (ANN). The study of the roots of A. pubescens was performed. The score matrix is obtained by principal component analysis, and the backpropagation artificial neural network (BP-ANN) model is established to identify the origin of the medicine based on LIBS spectroscopy of the roots of A. pubescens with three places of origin. The results show that the average classification accuracy is 99.89%, which exhibits better prediction of classification than linear discriminant analysis or support vector machine learning methods. To verify the effectiveness of PCA combined with the BP-ANN model, this method is used to identify the origin of C. pilosula. Meanwhile, the root and stem of L. wallichii are analyzed by the same method to distinguish the medicinal materials accurately. The recognition rate of C. pilosula is 95.83%, and that of L. wallichii is 99.85%. The results present that LIBS combined with PCA and BP-ANN is a useful tool for identification of Chinese herbal medicine and is expected to achieve automatic real-time, fast, and powerful measurements.