远程激光诱导击穿光谱技术分析岩石元素成分

远程激光诱导击穿光谱技术是一种利用脉冲激光和聚焦光路对远距离目标烧蚀击穿,获取目标等离子体光谱,定性或定量分析物质元素组成的光谱探测技术。设计并搭建了一套远程激光诱导击穿光谱系统。该系统结合卡式望远镜光学结构,实现探测2～10 m距离的目标、并可自动变焦。基于该系统提出一种远程探测岩石主要元素含量方法。通过对比实验,研究了脉冲能量、采集延时、积分时间、探测点累计探测次数对光谱信号的影响,确定了岩石谱线获得的最佳条件。选择48块岩石标本和6种常见国标岩石样品(页岩、花岗岩、安山岩、玄武岩、片麻岩、伟晶岩)进行LIBS实验。以原子光谱数据库为参考,根据岩石的主要元素提取特征谱线(SiⅠ390.55 nm,AlⅠ394.40 nm,AlⅠ396.15 nm,CaⅡ396.85 nm,FeⅠ404. 60 nm,SiⅠ500.60 nm,MgⅠ518.36 nm,NaⅠ589.59 nm)。利用偏最小二乘算法(PLS)建立岩石成分定量分析模型,将48块岩石标本作为训练集进行求解,并用六种国标岩石对模型进行检测,预测岩石Si和Al元素含量,平均误差分别为9.4%和9.6%。     

应用激光诱导击穿光谱检测污水溶液中的砷

工业冶炼过程中产生的废水中含有As等重金属元素,对环境造成污染并对人类身体健康形成危害,有必要对其进行实时、在线的监测。激光诱导击穿光谱(LIBS)是一种新型的元素测量技术,具有快速检测等优点。文章作者搭建了一套激光诱导击穿光谱实验装置,采用Nd∶YAG激光器产生的脉冲激光击穿样品产生等离子体,其发射的光谱被中阶梯光栅光谱仪分光,并用ICCD进行光电探测。对从现场采集的含砷工业废水开展了LIBS探测实验,并定性分析出了As元素的特征谱线。根据一系列含As浓度不同的污水样品的LIBS实验结果,获得元素浓度与谱线强度的关系曲线(定标曲线)。采用定标曲线可以对未知含As浓度的工业废水进行定量分析。结果表明,采用LIBS方法能够实现对污水溶液中的As元素的快速检测,具有广泛的应用前景。     

缅甸翡翠中铁元素的激光诱导击穿光谱定量检测

采用激光诱导击穿光谱(LIBS)技术定量分析缅甸翡翠中Fe元素的浓度。选择Fe元素的275.57 nm光谱线作为定量分析谱线,选取Si元素的288.17 nm光谱线作为内标谱线,选取12个缅甸翡翠样品作为研究对象,以其中9个样品绘制了传统定标法和内定标法的Fe元素定标曲线,并将定标曲线用于3个检验样品的Fe含量的实际预测。实验结果表明,采用传统定标方法时,定标样品光谱强度的相对标准偏差(RSD)在1.4%～8.3%之间,所建立的Fe元素浓度含量定标曲线的拟合相关系数R2为0.979,使用该方法建立的定标曲线对3个检验样品中Fe元素含量进行测定,最大相对误差为10.6%;而采用内定标法时,定标样品光谱强度的比值(I_Fe/I_Si)的相对标准偏差(RSD)在0.9%～5.7%之间,Fe的拟合相关系数R2达到0.989,样品中Fe元素的测定相对误差均可降低到7%以下。结果证明,利用内定标法定量分析翡翠中Fe的含量比传统定标法相对误差更小,采用LIBS技术结合内定标法更适于缅甸翡翠样品中Fe元素定量分析。     

激光诱导击穿光谱技术对土壤中重金属元素Cr的定量分析

为促进LIBS技术在土壤微量重金属元素检测中的应用,提高特征谱线的光谱强度和信背比,对实验参数进行优化,并对Cr元素进行分析。首先对激光器激发能量、样品距透镜距离和光谱仪采集延时等实验参数进行优化。对比激光器能量从60 mJ到110 mJ的谱线强度和信背比,当选用90 mJ的激发能量时可以得到最佳实验结果。其次,选择不同样品到透镜的距离,对比从焦前5 mm到焦后5 mm得到的实验结果,得出样品与透镜距离为焦后1 mm（即聚焦位置121 mm）时,Cr元素的特征谱线和信背比达到最佳。最后,分析对比光谱仪采集延时对谱线强度和信背比的影响,结果显示,与能量对等离子辐射强度的影响趋势大致相同,当采集延时为1 000 ns时,实验结果最佳。在最佳实验条件下（即激光器能量90 mJ、聚焦位置121 mm、采集延时1 000 ns）,对12种含有重金属Cr元素的土壤样品进行了光谱检测,为减弱外界环境的干扰,对同一样品的10个激光烧蚀位置得到的光谱做平均值预处理,选择Cr(Ⅰ)357.86 nm,Cr(Ⅰ)425.44 nm,Cr(Ⅰ)427.49 nm为特征谱线,通过建立样品掺杂浓度和光谱强度的定标曲线,得到了三条谱线的检测限LOD分别为74.62,64.07和67.49 mg·kg-1,拟合优度值R2分别为0.98,0.97和0.99,均方根误差值RMSE分别为0.41,0.33和0.35。同时,引入偏最小二乘法及支持向量机算法进一步提高了定标模型精度。研究表明,通过对实验参数进行优化及改善LIBS技术对微量元素的定量探测参数,得到了最优的光谱强度和信背比,并通过对Cr元素进行定量分析,计算定标曲线的Lorenz拟合得到检测限、拟合优度和均方根误差等实验参数,提高了LIBS对土壤中重金属元素的检测精度,这对于利用LIBS技术检测微量重金属元素具有重要的参考意义。     

复混肥中钾含量的激光诱导击穿光谱分析

将激光诱导击穿光谱技术(LIBS)应用于复混肥中的主要营养元素之一钾(K)元素的含量检测.样品中K养分的浓度较高,在等离子体形成过程中容易发生自吸收.通过分析谱线的激发能级、跃迁几率以及自吸收程度,确定最佳分析谱线为钾的原子线404.40 nm.同时为了提高LIBS分析复合肥样品的测量精度,分析了光谱测量稳定性随谱线信号平均次数的变化规律.结果显示,在本实验条件下,一次测量平均100个脉冲所得的光谱信号,其相对标准偏差较小.实验总共分析了9个复合肥样品,其中7个作为定标样品,建立K养分浓度的定标曲线,另外2个作为未知样品,用以检验LIBS分析K养分浓度的测量精确度.研究结果表明,定标曲线的线性拟合度为0.989,检验样品的绝对误差小于0.3%,体现了激光诱导击穿光谱技术快速分析复混肥中钾养分的潜力.     

LIBS技术结合多元校正定标检测土壤中的Cr

激光诱导击穿光谱(LIBS)技术结合支持向量机(SVM)定量分析土壤中Cr元素的含量。利用波长为1 064 nm的Nd∶YAG脉冲激光器作为激发光源,采用光栅光谱仪和CCD分光探测不同重金属元素含量土壤样品的LIBS特征光谱。为了提高土壤中Cr元素定量分析的精度,分别采用多元线性回归分析和SVM两种方法对土壤中Cr元素的含量进行定量分析。研究结果表明,采用多元线性回归分析方法可以有效提高定量分析的精度,定标曲线拟合相关系数从传统定量分析方法的0.689提高到0.980;SVM定量分析方法训练集得到的定标曲线斜率近似为1,拟合相关系数为0.998,优于传统定量分析方法和多元线性回归分析方法,对检验集的预测相对误差均在2.57%以内。LIBS技术结合多元线性回归和SVM定量分析方法可以有效的提高土壤中Cr元素定量分析的稳定性和精度,校正土壤基体效应对Cr元素定量分析的影响。     

基于LIBS技术的钢铁合金中元素多变量定量分析方法研究

针对钢铁合金样品元素组成相对复杂,基体效应较严重的问题,利用激光诱导击穿(LIBS)光谱技术对钢铁合金中的元素进行了定量分析。以Nd∶YAG脉冲激光器基频1 064 nm波长激光作为激发光源,采用中阶梯光栅光谱仪和ICCD分光探测钢铁合金样品的LIBS光谱。通过优化实验确定最佳探测延时为1.5 μs,最佳探测门宽为2 μs,激光聚焦点位置在实验样品靶面以下1.5 mm。采用单变量定量分析、多变量线性回归和偏最小二乘(PLS)三种方法分析钢铁合金中Cr元素和Ni元素的含量。结果表明,采用单变量定标方法定标曲线相关系数不高,对待测样的预测误差相对较大,难以有效地定量分析基体元素复杂的钢铁合金中金属元素的含量;采用多变量线性回归分析方法能有效提高定量分析的精度;采用PLS方法得到的Cr和Ni元素的拟合曲线相关系数r分别为0.981和0.995,对两个待测样品中Cr元素和Ni元素的预测相对误差在6.4%和7.1%以内,分析结果优于多变量线性回归方法。可见,采用多变量校正的PLS方法能更有效地校正基体效应对定量分析的影响,提高定量分析的精度。     

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%。     

激光击穿光谱检测赣南脐橙中铬元素的实验研究

为评估激光诱导击穿光谱技术(LIBS)对水果样品中重金属元素的检测潜力,选用在不同浓度梯度重铬酸钾水溶液中浸泡了30个小时的赣南脐橙样品进行LIBS实验,采集铬元素的特征谱线与峰值强度信息。在激光照射部位称取3 g左右的脐橙样品进行湿法消解,用原子分光光度计检测样品中的铬浓度。实验数据用Origin软件进行拟合后得到了谱线峰值强度和Cr浓度之间的关系曲线,即定标曲线,二者有线性关系,线性相关度0.981 66。由检测限公式计算得到铬浓度的检测限为11.68 μg·g-1。采用该定标曲线即可对赣南脐橙中的铬元素进行定量检测。实验结果表明LIBS技术是一种检测、定量分析水果样品中重金属元素含量的有效手段。     

激光诱导击穿光谱结合多元非线性方法定量分析土壤中锰

锰元素是植物所需的微量元素之一。采用激光诱导击穿光谱(laser-induced breakdown spectroscopy,LIBS)技术对土壤中锰元素进行定量分析。以46个土壤样品为研究对象,获取土壤激光诱导击穿光谱数据,选取锰元素403.1 nm的特征谱线为分析线。根据谱线强度与元素浓度建立定标曲线,相关系数仅为0.78,定标结果说明,由于土壤样品成分的复杂性,锰元素浓度受土壤基体效应影响严重,应根据锰元素在土壤中的存在形式,选取相关元素,建立多元非线性回归定量分析方法,消除基体效应,从而提高LIBS测量的准确性。在多元非线性回归方法中分别考虑碳和铁元素对锰元素浓度的影响。与定标曲线相比,在考虑碳和铁元素对锰元素影响时,LIBS预测浓度与参考浓度的相关系数为0.97,相对误差为3.2%～10.3%,测量的准确度得到提高。实验结果表明,将多元非线性回归方法和激光诱导击穿光谱技术结合可以对土壤中微量锰元素进行定量分析。     

High Precision Identification of Igneous Rock Lithology by Laser Induced Breakdown SpectroscopySCIEI北大核心CSCD

In the field of petroleum exploration, lithology identification of finely cuttings sample, especially high precision identification of igneous rock with similar property, has become one of the geological problems. In order to solve this problem, a new method is proposed based on element analysis of Laser-Induced Breakdown Spectroscopy (LIBS) and Total Alkali versus Silica (TAS) diagram. Using independent LIES system, factors influencing spectral signal, such as pulse energy, acquisition time delay, spectrum acquisition method and pre-ablation are researched through contrast experiments systematically. The best analysis conditions of igneous rock are determined: pulse energy is 50 mJ, acquisition time delay is 2 mu s, the analysis result is integral average of 20 different points of sample's surface, and pre-ablation has been proved not suitable for igneous rock sample by experiment. The repeatability of spectral data is improved effectively. Characteristic lines of 7 elements (Na, Mg, Al, Si, K, Ca, Fe) commonly used for lithology identification of igneous rock are determined, and igneous rock samples of different lithology are analyzed and compared. Calibration curves of Na, K, Si are generated by using national standard series of rock samples, and all the linearly dependent coefficients are greater than 0.9. The accuracy of quantitative analysis is investigated by national standard samples. Element content of igneous rock is analyzed quantitatively by calibration curve, and its lithology is identified accurately by the method of TAS diagram, whose accuracy rate is 90.7%. The study indicates that LIBS can effectively achieve the high precision identification of the lithology of igneous rock.     

土壤中重金属元素的双脉冲激光诱导击穿光谱研究

基于正交预烧蚀双脉冲激光诱导击穿光谱(DP-LIBS) 技术对长春市四个地点地表土壤样品中的重金属元素进行了研究, 根据光谱线强度定性分析了重金属元素Mn, Cr, Cu, Pb含量.实验结果发现, 在532和1064 nm激光脉冲能量分别为70和100 mJ的条件下光谱增强随延时的变化出现双峰结构. 脉冲间延时20 μs时, Mn I 406.4 nm光谱增强幅度达到2.75倍, 延时为30 μs时出现第二个尖峰, 增强幅度为2.4倍.最后对正交预烧蚀DP-LIBS光谱增强机理进行了讨论. 关键词： 预烧蚀 双脉冲激光诱导击穿光谱 光谱增强 土壤污染     

Analysis of Minerals and Rocks by Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) technique was applied for rapid analysis of major and minor elements composing geological samples including minerals, rocks, and a soil sample. The plasma was produced in air at atmospheric pressure by focusing on the targets a pulsed infrared Nd:YAG laser in open-path configuration. The emitted light in the UV-Vis was analyzed by a compact LIBS system to measure spectral emission lines of Si, Al, Fe, Ca, Na, K, Mg, C, Cu, Mn, and Ti. The experimental issues relevant for the analysis of the different samples were investigated by taking into account their peculiar features: drilling through a weathered layer, roughness and grain-size considerations, statistical averaging, and accuracy of the measurements. In this approach, the characterization of the samples was achieved by studying the relative variations of the emission intensities of each element normalized with respect to an internal standard. The present study shows the usefulness of LIBS as a tool for reliable identification of field samples.     

Comparative Study of Two Methods of Orthogonal Double-Pulse Laser-Induced Breakdown Spectroscopy of Aluminum

Double-pulse laser induced breakdown spectroscopy (DP-LIBS) of aluminum sample is studied experimentally in orthogonal configuration in air. In this configuration, two schemes of reheating and pre-ablation are examined and the results are compared with single pulse one. The effect of delay time between two laser pulses on emission line intensities of plasma is investigated. Some of the parameters that have been involved in different mechanism of signal enhancement such as plasma temperature, sample heating effects, atmospheric effects, and modification of the ablation dynamics are more discussed. Investigation of the effect of laser pulse energy on emission line intensities in single pulse LIBS experiment demonstrate that because of saturation effects the intensities will not increase necessarily by increasing the laser pulse energy. Moreover, the results show that the electron temperature and rate of mass removal in orthogonal configuration of DP-LIBS is higher than that of single pulse with the same total energy. It is suggested that for correct comparison between single and double pulse results, the optimum pulse energy in single pulse should be considered. Overall, our results demonstrate that under optimized conditions the signal enhancement is much more in pre-ablation configuration than re-heating configuration.     

利用激光诱导击穿光谱分析土壤成份

 搭建了一套激光诱导击穿光谱实验装置,并通过配置特定样品,开展了一系列激光诱导击穿光谱探测实验。根据含有不同质量分数的同种元素样品的激光诱导击穿光谱实验结果,获得元素质量分数与谱线强度的关系曲线(定标曲线)。对中南民族大学附近的土壤进行激光诱导击穿光谱实验,发现土壤中含有Mg,Ca,Na等18种元素,对河南云台山茱萸峰岩石的激光诱导击穿光谱实验结果仅获得Fe,Mg,Ca 3种金属元素。比较这2种实际样品的激光诱导击穿光谱结果表明,检测样品的物理结构影响激光诱导光谱的实验结果。     

基于LIBS技术结合PCA-SVM机器学习对猪肉部位的识别研究

近年来,激光诱导击穿光谱（LIBS）与算法相结合分类、识别生物组织逐渐兴起。由于猪肉各部位组织光谱特性相似,仅通过分析光谱信息很难达到准确识别的效果,采用来自于同一个体、四个不同部位的猪肉进行研究,并将其进行切片、压平,应用LIBS技术对4种部位的组织（里脊,梅花,前腿,五花）进行了样品光谱的采集,每种样品采集100幅光谱进行分析,选取Ca,Na,K等6条谱线进行了初步光谱分析,观测谱线发现除脂肪含量较多的五花组织C-N以及C含量较其他组织高以外,其他组织很难区分,进一步对这6个成分进行主成分分析（PCA）,得到PC1,PC2,PC3累计贡献率达到95%,通过特征分数作为支持向量机（SVM）模型输入源,建立SVM分类模型,得到几种部位样品的混淆矩阵图,通过观察混淆矩阵可以清楚分辨出每个种类样品的分类整准确率,发现四种样品准确率分别为96%,98%,97%,100%,平均准确率达到了97%以上。研究证明LIBS结合PCA-SVM可作为一种快速鉴别猪肉不同组织部位的检测方法。     

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.     

Calibration-free laser-induced breakdown spectroscopy for quantitative elemental analysis of materials

The application of calibration-free laser-induced breakdown spectroscopy (CF-LIBS) for quantitative analysis of materials, illustrated by CF-LIBS applied to a brass sample of known composition, is presented in this paper. The LIBS plasma is produced by a 355?nm pulsed Nd:YAG laser with a pulse duration of 6?ns focussed onto a brass sample in air at atmospheric pressure. The time-resolved atomic and ionic emission lines of Cu and Zn from the LIBS spectra recorded by an Echelle spectrograph coupled with a gated intensified charge coupled detector are used for the plasma characterization and the quantitative analysis of the sample. The time delay where the plasma is optically thin and is also in local thermodynamic equilibrium (LTE), necessary for the elemental analysis of samples from the LIBS spectra, is deduced. An algorithm relating the experimentally measured spectral intensity values with the basic physics of the plasma is developed. Using the algorithm, the Zn and Cu concentrations in the brass sample are determined. The analytical results obtained from the CF-LIBS technique agree well with the certified values of the elements in the sample, with an accuracy error <1%.