LIBS技术在污染土壤重金属含量分布测量中的应用

诱导击穿光谱技术(LIBS)具有实时快速、多元素同时探测的优势,并且无需样品预处理,检测成本低,是土壤重金属定量分析检测的一种重要分析手段。将LIBS技术应用于冶炼厂区周围土壤中重金属的含量分布分析研究,利用Cu,Pb和Cr三种元素的特征谱线强度分析了冶炼厂区周围土壤中Cu,Pb和Cr三种元素的含量分布。实验结果表明冶炼厂区土壤LIBS光谱中Cu和Pb两种元素的特征谱线强度分布与实际含量分布呈较好的线性关系,而Cr元素的特征谱线强度分布与实际含量分布相关性较差。为了提高Cr元素含量分布分析的准确性,利用CF-LIBS结合Saha方程应用于土壤Cr元素的含量分布分析中。实验结果表明基于CF-LIBS计算的Cr和Si两种元素含量比值分布与土壤Cr元素的实际含量分布之间具有良好的一致性。相比于其他的化学分析方法,LIBS技术结合CF-LIBS可以快速的对区域土壤重金属元素的含量分布进行检测,因此将LIBS技术与CF-LIBS相结合用于土壤重金属的含量分布检测中,为污染区域的重金属防治提供方向。     

Contaminant concentration in environmental samples using LIBS and CF-LIBS

The present paper deals with the detection and quantification of toxic heavy metals like Cd, Co, Pb, Zn, Cr, etc. in environmental samples by using the technique of laser-induced breakdown spectroscopy (LIBS) and calibration-free LIBS (CF-LIBS). A MATLAB^TM program has been developed based on the CF-LIBS algorithm given by earlier workers and concentrations of pollutants present in industrial area soil have been determined. LIBS spectra of a number of certified reference soil samples with varying concentrations of toxic elements (Cd, Zn) have been recorded to obtain calibration curves. The concentrations of Cd and Zn in soil samples from the Jajmau area, Kanpur (India) have been determined by using these calibration curves and also by the CF-LIBS approach. Our results clearly demonstrate that the combination of LIBS and CF-LIBS is very useful for the study of pollutants in the environment. Some of the results have also been found to be in good agreement with those of ICP-OES.     

The validity of commercial LIBS for quantitative analysis of brass alloy — comparison of WDXRF and AAS

Commercial low-cost laser induced breakdown spectroscopy (LIBS) has been successfully employed for the quantitative analysis of a Cu-based alloy using a Nd:YAG laser at 1064 nm. The main aim of the present investigation is to explore the benefits of a commercial low-cost LIBS setup. It was recognized that some trace elements such as Al and S could not be detected by LIBS even with a high-resolution spectrometer. The main difficulties in quantifying Cu as a basic component of a brass alloy are related to the self-absorption of Cu spectral lines, with the effect complicated at Cu concentrations higher than 65%. However, few Cu lines such as that at 330.795 nm would be helpful to use due to their lower susceptibility to self-absorption. LIBS, flame atomic absorption spectrometry (FAAS), and wavelength dispersive X-ray fluorescence (WDXRF) were compared for the detection of major and trace metals in the Cu-based alloy. In the case of WDXRF, the brass samples were identified by using a standardless quantitative analysis program depending on a fundamental parameter approach. The quantitative analysis results were acceptable for most of the major and minor elements of the brass sample. Therefore, commercial low cost LIBS would be useful for quantitative analysis of most elements in different types of alloys.     

Element analysis of complex materials by calibration-free laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is a promising method for fast and quantitative element analysis of complex materials. We report on LIBS measurements of multi-component oxide materials and the compositional analysis of materials by a calibration-free (CF) method. This CF-LIBS method relies on modeling of the optical emission of laser-induced plasma assuming local thermodynamic equilibrium. Various materials are investigated and the calculated concentration values (C _CF) of oxides CaO, Al₂O₃, MgO, SiO₂, FeO, and MnO are in agreement with nominal concentration values (C _N) from reference analysis. The relative error in oxide concentration e _r=|C _CF?C _N|/C _N decreases with increasing concentration. The quantification is limited to major oxides (C _N≥1 wt%). Slag samples from industrial steel production are analyzed on site by means of a mobile measurement system. LIBS measurements are performed at different sample temperatures. The results obtained show that CF-LIBS is applicable to fast compositional analysis of complex materials in harsh environments.     

金纳米与磁场作用下LIBS检测灵敏度改善研究

针对激光诱导击穿光谱技术（LIBS）中等离子体的发射光谱增强问题,提出一种磁场增强LIBS与纳米颗粒增强LIBS（NELIBS）相结合的方法。采用热蒸发法在样品表面沉积一层直径20 nm的金纳米颗粒。利用波长为1 064 nm,最大能量为200 mJ的Nd∶YAG脉冲激光器在室温,一个标准大气压下对纯铜和黄铜进行诱导击穿。调整激光能量为30~110 mJ,分别使用传统LIBS、磁场增强LIBS、NELIBS以及两种方法结合对纯铜进行激光诱导击穿,得到特征谱线(Cu Ⅰ 521.8 nm)的强度增强因子和信噪比,并对其增强机理进行分析。在相同环境下使用四种方式对黄铜和纯铜进行诱导击穿以探测样品中的微量元素。当在样品表面沉淀金纳米颗粒或者将沉淀有金纳米颗粒的样品放在磁场中进行诱导击穿时,发现纯铜样品的光谱中存在Mg元素的特征谱线Mg Ⅱ 279.569 nm,黄铜样品的光谱中存在Si元素的特征谱线 Si Ⅰ 251.611 nm。实验结果表明：单独施加磁场约束或增加纳米金颗粒均可以有效增强等离子体光谱强度,但增强效果弱于两种方法结合,磁场约束对光谱的增强效果弱于NELIBS的增强效果。当结合NELIBS与磁场约束LIBS时,谱线增强因子最高可达14.3(Cu Ⅰ 521.8 nm),相比于磁场增强LIBS和NELIBS,最大增强因子分别提高了28%和59%。四种情况中当激光脉冲能量逐渐增大时,等离子体向外膨胀的强度增大,磁场产生的洛伦兹力束缚等离子的能力相对减弱,同时纳米金颗粒对等离子体发射光谱的增强作用被削弱,谱线强度降低,等离子体的增强因子逐渐减小后趋于稳定。通过NELIBS与磁场约束LIBS结合方式,不仅可以有效提高等离子体的发射谱线强度,改善光谱信号信噪比,而且传统LIBS方法中由于谱线强度低、背景噪声大而无法探测的微量元素可以被探测到,LIBS技术对微量元素的探测能力得到显著提高,微量元素的探测下限变得更低。NELIBS与磁场约束LIBS结合的方法具有更高的灵敏度和准确度,为激光诱导击穿光谱技术的谱线增强方法提供了新的思路,在该领域具有广阔的应用前景。     

Quantitative analysis of bronze samples by laser-induced breakdown spectroscopy (LIBS): A new approach, model, and experiment

A new approach to the quantitative elemental analysis of alloys by means of laser-induced breakdown spectroscopy (LIBS) is proposed. The disproportion between the element stoichiometry and spectral intensities is attributed to selective evaporation of components during the heating-melting-evaporation stage. The proposed correction to plasma spectra with account for the Prokhorov-Bunkin melt transparency wave ensures a good agreement between the relative intensities of LIBS analytical lines [(nm): Cu, 511; Zn, 472; Sn, 286; Pb, 406] and the alloy stoichiometry for five samples of four-component bronze measured in various regimes of plasma excitation and signal detection. A criterion is formulated to select the analytical lines, for which the concentration of elements is proportional to the constant of the process and the intensity of the corrected lines.     

基于自吸收量化的激光诱导等离子体表征方法

为了表征激光诱导等离子体的定量特征参数,提出了一种谱线自吸收量化的方法,通过获得分析元素谱线的半高全宽来量化谱线自吸收程度,进而得到等离子体的特征参数,包括电子温度、元素含量比以及辐射物质的绝对数密度.与传统激光诱导击穿光谱定量分析方法相比,新方法由于计算过程与谱线强度弱相关,所以分析结果基本不受自吸收效应的影响,同时也无需额外的光谱效率校准.基于铝锂合金的实验结果表明,该方法能够实现精确的相对定量分析和等离子体的特性诊断.     

Spectroscopy of laser-produced plasmas: Setting up of high-performance laser-induced breakdown spectroscopy system

It is a well-known fact that laser-induced breakdown spectroscopy (LIBS) has emerged as one of the best analytical techniques for multi-elemental compositional analysis of samples. We report assembling and optimization of LIBS set up using high resolution and broad-range echelle spectrograph coupled to an intensified charge coupled device (ICCD) to detect and quantify trace elements in environmental and clinical samples. Effects of variations of experimental parameters on spectroscopy signals of copper and brass are reported. Preliminary results of some plasma diagnostic calculations using recorded time-resolved optical emission signals are also reported for brass samples.     

Femtosecond laser-induced Cu plasma spectra at different laser polarizations and sample temperatures

Laser-induced breakdown spectroscopy (LIBS) is a good technique for detecting and analyzing material elements due to the plasma emission produced by the high-power laser pulse. Currently, a significant topic of LIBS research is improving the emission intensity of LIBS. This study investigated the effect of laser-polarization on femtosecond laser-ablated Cu plasma spectra at different sample temperatures. The measured lines under circularly polarized lasers were higher than those under linearly and elliptically polarized lasers. The enhancement effect was evident at higher Cu temperatures when comparing the plasma spectra that have circular and linear polarizations for different target temperatures. To understand the influence of laser-polarization and sample temperature on signal intensity, we calculated the plasma temperature (PT) and electron density (ED) . The change in PT and ED was consistent with the change in the atomic lines as the laser polarization was being adjusted. When raising the Cu temperature, the PT increased while the ED decreased. Raising the Cu temperature whilst adjusting the laser-polarization is effective for improving the signal of femtosecond LIBS compared to raising the initial sample temperature alone or only changing the laser polarization.     

样品温度对纳秒激光诱导Cu等离子体特征参数的影响

为了研究样品温度对激光诱导击穿Cu等离子体特征参数的影响,以黄铜为研究对象,在优化的实验条件下采用波长为532 nm的Nd∶YAG纳秒脉冲激光诱导激发不同温度下的块状黄铜,测量了Cu等离子体的特征谱线强度和信噪比;同时在局部热平衡条件下利用Boltzmann斜线法和Stark展宽法分析计算了不同的样品温度条件下等离子体电子温度和电子密度。实验结果表明,在激光功率为60 mW时,随着样品温度的升高,Cu的特征谱线强度和信噪比逐渐增加,样品温度为130 ℃时达到最大值,然后趋于饱和。计算表明,黄铜样品中Cu元素Cu Ⅰ 329.05 nm,Cu Ⅰ 427.51 nm,Cu Ⅰ 458.71 nm,Cu Ⅰ 510.55 nm,Cu Ⅰ 515.32 nm,Cu Ⅰ 521.82 nm, Cu Ⅰ 529.25 nm,Cu Ⅰ 578.21 nm八条谱线在130℃的相对强度相较于室温（18 ℃）下分别提高了11.55倍、4.53倍、4.72倍,3.31倍、4.47倍、4.60倍、4.25倍、4.55倍,光谱信噪比分别增大了1.35倍,2.29倍、1.76倍、2.50倍、2.45倍、2.28倍、2.50倍,2.53倍。分析认为,升高样品温度会增大样品的烧蚀质量,相对于温度较低状态增加了等离子体中样品粒子浓度,进而提高等离子体发射光谱强度。所以,适当升高样品温度能够提高谱线强度和信噪比,从而增强LIBS技术检测分析光谱微弱信号的测量精度,改善痕量元素的检测灵敏度。同时研究了改变样品温度时等离子体电子温度和电子密度的变化趋势。计算表明,当样品温度从室温上升到130 ℃的过程中,等离子体的电子温度由4 723 K上升到7 121 K时基本不再变化。这种变化规律与发射谱线强度和信噪比变化趋势一致。分析认为,这主要是由于在升高样品温度的初始阶段,激光烧蚀量增大,等离子体内能增大,从而导致等离子体电子温度升高。当激光烧蚀样品的量达到一定值后不再变化,激光能量被激发溅射出来的样品蒸发物以及尘粒的吸收、散射和反射,导致激光能量密度降低,电子温度趋于饱和,达到某种动态平衡。选用一条Cu原子谱线（324.75 nm）的Stark展宽系数计算激光等离子体的电子密度,同时研究改变样品温度时等离子电子密度的变化趋势,计算表明在样品温度为130 ℃时,Cu Ⅰ 324.75 nm对应的等离子电子密度相较于室温（18 ℃）条件下增大了1.74×1017 cm-3。该变化趋势与电子温度的变化趋势一致。适当升高样品温度使得电子密度增大,从而提高电子和原子的碰撞几率,激发更多的原子,这是增强光谱谱线强度的原因之一。由此可见,升高样品温度是一种便捷的提高LIBS检测灵敏度的有效手段。     

基于内标CF-LIBS的混合水溶液中多金属元素的定量分析

提出一种简化内标自由定标激光诱导击穿光谱(CF-LIBS)分析方法,并应用于混合水溶液中Cr、Mn、Pb、Cd、Ca、Al、Co等金属元素绝对浓度的定量分析.实验结果表明,在最优化实验参数下产生的激光等离子体满足局部热平衡和光学薄条件,由该分析方法得到的LIBS检测精确度明显优于采用液固转换后的传统CF-LIBS方法,测定的浓度值与配置值的相对误差小于1%,说明应用该内标CF-LIBS方法能够同时精确测定液相基质中的多种微量金属元素的含量.     

基于共振与非共振双线的自吸收免疫LIBS技术研究

激光诱导击穿光谱(LIBS)定量分析中的自吸收效应不仅会降低谱线强度和增加线宽,而且使定标结果饱和,从而影响最终的分析精度。为了消除该效应的影响,提出了一种基于共振双线与非共振双线选择的自吸收免疫激光诱导击穿光谱(SAF-LIBS)技术,通过比较所测谱线强度比值和理论强度比值来确定等离子体的光学薄时刻,并使用共振线与非共振线来拓展元素含量的可测量范围。该技术可以分为定标和定量两个分析过程,其定标过程为:计算待测元素的共振双线及非共振双线的理论强度比,通过对比不同待测元素含量样品的共振双线及非共振双线在不同延时下的强度比和理论比,确定等离子体的光学薄时刻;使用一系列标准样品建立LIBS非共振线的单变量定标曲线;利用准光学薄谱线建立共振线和非共振线的SAF-LIBS单变量分段定标曲线。其定量分析过程为:先用非共振线和LIBS定标曲线确定未知样品所属的含量分段,再用准光学薄谱线以及与所属分段的共振或非共振SAF-LIBS定标曲线完成定量分析。对Cu元素的单变量定标结果表明,对于共振线,最佳延时随着样品含Cu量的增加而增加,且只有当含Cu量低于0.05%时,才可能获得准光学薄的共振线,而随着Cu含量的增加,自吸收变得非常严重,以至于无法获得光学薄的共振线;对于非共振线,当含Cu量在0.01%~30%范围内,均可获得准光学薄的非共振谱线,而当Cu含量大于50.7%时,将无法在等离子体寿命期内捕获到光学薄谱线。对Cu元素的定量分析结果表明,基于共振双线与非共振双线的自吸收免疫LIBS技术可以有效地避免自吸收效应的影响,各分段定标曲线的线性度均大于0.99,对两个未知样品中Cu元素含量的绝对测量误差分别为0.01%和0.1%,探测限达到了1.35×10-4%,最大可测量范围拓展至50.7%。     

利用激光诱导击穿光谱对铝合金成分进行多元素同时定量分析

利用激光诱导击穿光谱定量分析了铝合金中多种元素的成分。采用Nd∶YAG脉冲激光器,在空气环境下烧蚀铝合金固体样品获得等离子体。利用多通道光栅光谱仪和CCD检测器对200～980 nm波长范围的光谱进行同时检测。研究了检测时延、激光脉冲能量、元素深度分布对光谱强度的影响,考虑这些因素之后对实验参数进行了优化。在优化的实验参数下对国家标准铝合金样品中的八种元素Si,Fe,Cu,Mn,Mg,Zn,Sn及Ni进行了定标,并利用定标曲线对一种铝合金样品进行了定量分析。实验结果表明,测量结果的相对标准偏差(RSD)最大为5.89%,相对误差在-20.99%～15%范围内,说明对铝合金样品成分进行定量分析,激光诱导击穿光谱是一种有效的光谱分析工具,但是分析结果的准确度仍需要提高。     

In situ multielemental monitoring in coral skeleton by CF-LIBS

Corals contain organic constituents identical to that of human skeleton, including Ca, Sr, Mg, Na, K, etc. Calibration-Free Laser-Induced Breakdown Spectroscopy (CF-LIBS) technique has been applied for quantitative estimation of the elements in coral samples. Laser-induced plasma emission at the sample surface, without any pretreatment, has been used for recording the spectra. The stoichiometric ablation and LTE criteria have been validated for the application of CF-LIBS. A data processing program in MATLAB for CF-LIBS has been developed for the determination of Ca, Sr, Mg, C, O, Na, K, and Fe concentration in these coral samples.     

Quantitative analysis of ITO film by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is an effective method for nondestructive rapid element analysis in a wide range of media in situ. We use the LIBS technique for quantitative analysis of indium tin oxide (ITO) films, which are transparent conducting materials widely used in industry. The plasma is generated by focusing a Nd:YAG laser pulse with a duration of 10 ns and a wavelength of 1064 nm onto the ITO-sample surface. We perform test experiments to define optimum values of the laser-pulse energy and the time delay between the laser pulse and the beginning of the LIBS spectra acquisition. Next, by the calibration-free Boltzmann plot method, we assess the plasma temperature and finally calculate the content of In and Sn in the test ITO specimen, and this agrees well with real concentration values.     

基于LIBS与化学计量学的植物叶片分类研究

激光诱导击穿光谱（LIBS）是一种高效快速的光谱采集手段,可应用于各类物质的元素分析工作中。线性判别分析（LDA）与支持向量机（SVM）是化学计量学中两种常用的有监督算法,均通过对已知不同种类的样本数据进行学习建模,进而实现对未知类别数据的归类。为了实现LIBS技术对有机物的高准确率识别,将这两种算法应用到LIBS光谱数据的分类中。实验利用波长为1 064 nm的纳秒激光烧蚀女贞、珊瑚树、竹子三种植物的叶片,并采集每种树叶220～432 nm波段的100组光谱数据。通过对300组样本的原始光谱数据进行主成分提取,由第一主成分（PC1）和第二主成分（PC2）的得分图得出三种植物光谱的相似度非常高。然后,利用每种叶片70组样本的光谱数据作为训练集建模,其余30组光谱数据作为测试集来进行树叶种类的预测识别。将PCA对原始光谱数据提取得到的前20个主成分作为LDA与SVM建模的属性值。对于LDA算法,将属性值分析后得到前两个判别函数值,通过聚类分析发现不同种类的植物叶片光谱数据在空间上的分离效果较好,同一种类基本聚集在一起。再借助马氏距离可得到测试集的平均分类正确率为96.67%。与此类似,使用SVM方法对训练集样本的数据进行学习得到分类超平面,对测试集的平均分类正确率达到98.9%。研究结果表明,经过PCA对数据的预处理,再结合LDA,SVM这两种方法可实现LIBS技术应用于复杂有机物的快速准确分类,并且PCA与SVM结合的分类正确率更高。该方法可在食品快速溯源、生物组织原位鉴别、有机爆炸物远程分析等领域应用。     

纳秒激光诱导紫铜黄铜等离子体特征参数的对比研究

基于1064 nm Nd:YAG激光器,对比研究了紫铜和黄铜等离子的特征参数。洛仑兹函数拟合Cu I 324.75 nm得到紫铜和黄铜等离子体的电子密度分别是3.61017 cm-3和3.31017 cm-3。为了减小谱线自发辐射跃迁几率不确定性和测量误差带来的计算误差,采用改进型迭代玻耳兹曼算法精确求解紫铜等离子体和黄铜等离子体的电子温度分别是6316 K和6051 K,分析表明,两种等离子体特征参数的差异主要是由于黄铜中的锌元素的电离能（9.39 eV）大于铜元素的电离能（7.72 eV）而造成的。实验数据证实激光诱导的紫铜和黄铜等离子体满足局部热力学平衡模型和光学薄模型。     

Laser-induced breakdown spectroscopy: technique,new features,and detection limits of trace elements in Al base alloy

Laser-induced breakdown spectroscopy (LIBS) has proven to be extremely versatile, providing multielement analysis in real time without sample preparation. The principle is based on the ablation of a small amount of target material by interaction of a strong laser beam with a solid target. The laser must have sufficient energy to excite atoms and to ionize them to produce plasma. We aimed to improve the LIBS limit of detection (LOD) and the precision of spectral lines emitted from the produced plasma by optimizing the parameters affecting the LIBS technique. LIBS LOD is affected by many experimental parameters such as interferences, self-absorption, spectral overlap, signal-to-noise ratio, and matrix effects. The plasma in the present study is generated by focusing a 6-ns pulsed Nd–YAG laser at the fundamental wavelength of 1,064 nm onto the Al target in air at atmospheric pressure. The emission spectra are recorded using an SE 200 Echelle spectrometer manufactured by the Catalina Corporation; it is equipped with an ICCD camera type Andor model iStar DH734-18. This spectrometer allows time-resolved spectral acquisition over the whole UV-NIR (200–1,000 nm) spectral range. Calibration curves for Cu, Mg, Mn, Si, Cr, and Fe were obtained with linear regression coefficients around 99 % on the average in aluminum standard alloy samples. The determined LOD has very useful improvements for Cu I at 521.85 nm, Si I at 288.15 nm, Mn I at 482.34 nm, and Cr I at 520.84 nm spectral lines. LOD is improved by 83.8 % for Cu, 49 % for Si, 84.3 % for Mn, and 45 % for Cr lower with respect to the previous works.     

Emission spectroscopy of laser ablation plume: Composition analysis of a target in water

Emission spectra of the laser ablation plume formed by the irradiation of Cu65/Zn35 binary alloy in water at the room temperature with 150-ns pulsed laser were measured. The spectra were analyzed by comparing with the theoretical calculation based on the assumption that self-absorption effect is negligible and that the same temperature can be applied to Cu atoms and Zn atoms in the plume. The calculation reproduced the spectra very well and gave reasonable temperature as a best-fit parameter. However, the best-fit value of the Cu atomic density relative to Zn is significantly low compared with the target composition. Care should be taken to perform in situ LIBS in liquid due to the complicated plume formation mechanism and dynamics of material intake into the plume.     

自动聚焦激光诱导击穿光谱远程测量系统

激光诱导击穿光谱(LIBS)技术具有非接触测量、无需样品预处理以及快速多元素同时分析等特点,适合于高温、高压、真空、有毒以及敌对环境等仪器和操作人员无法靠近观测对象的应用中。LIBS技术结合望远镜系统可以实现物质成分的远距离检测与分析。搭建了一套可自动聚焦的LIBS远程测量系统。该系统中的望远镜采用Schwarzschild结构,由一块凹球面反射镜和一块凸球面反射镜组成。两块球面反射镜共轴安装。其中凸面反射镜安装在电控精密平移台上,电动平移台可带动凸面反射镜沿光轴移动。通过调整凸面反射镜的位置,改变凸面反射镜和凹面反射镜的间距,进而改变系统的焦距,实现对不同距离的样品进行光谱测量。该结构的优点在于：激光聚焦光路与信号光采集光路相同,便于安装和调试;望远镜系统采用全反射式光路,适用于紫外波段检测;只包括两个球面反射镜,结构紧凑,元件容易加工。望远镜系统调焦距离为1.5～3.6 m,聚焦光斑直径约为0.5~1.0 mm。使用该系统对铜样品进行了LIBS实验,确认了Cu元素的特征谱线。通过测量Cu元素的LIBS特征谱线(Cu Ⅰ 223.01 nm, Cu Ⅰ 224.43 nm)峰面积和反射镜间距之间关系,得到了激光的最优聚焦位置。实验结果表明,该系统能够完成样品的远程激发和LIBS光谱测量,并能够对不同距离的样品进行自动聚焦。