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.     

Analytical Assessments of Gallstones and Urinary Stones: A Comprehensive Review of the Development from Laser to LIBS

Abstract

Laser-induced breakdown spectroscopy (LIBS) is a sensitive optical technique capable of fast multi-elemental analysis of various kinds of materials (solid, liquids, and gases) and its applications are growing rapidly and continue to extend to include a broad variety of biological materials. Its application is suited particularly for urinary stones and gallstones bulk analysis and microanalysis because investigation of the spatial distribution of matrix and trace elements can help to explain their emergence and growth. Therefore, we review the application of LIBS for the analysis of different kinds of gallstones and urinary stones. In brief, we also describe the history, fundamentals, advantages, and disadvantages of LIBS and its potential for spectrochemical analysis of gallstones and kidney stones. We also emphasize the applications of different kinds of lasers in urology, particularly the laser ablation of gallstones and urinary stones and its recent progress. We also summarize and compare the analytical figures of merits of analytical techniques that are commonly used to characterize and/or analyze stones.     

样品物理方法前处理提高猪肉中Pb元素的LIBS分析精度研究

农产品基体复杂,为了减弱水分和有机质对其痕量重金属元素LIBS检测能力的影响,以期提高目标元素LIBS分析灵敏度和预测精度。以实验室含Pb溶液污染处理的新鲜猪肉样品为例,对猪肉样品进行烘干、粉碎、压片处理,比较样品简单的物理方法前处理提高目标元素LIBS探测效果的可行性。通过采集猪肉鲜样和干样的LIBS谱线信息发现,鲜样受水分、有机质成分影响致使其谱线信息背景和噪声信号干扰较大;对于10个浓度梯度的样品,目标元素特征谱线Pb Ⅰ 405.78的LIBS强度信息在鲜样中无明显的差异性,而在干样样品中差异明显并表现出一定的梯度关系。说明LIBS缺乏对鲜样样品低浓度Pb污染的探测能力,干燥处理削弱了水分的影响、浓缩了样品浓度范围,提高了LIBS的检测灵敏度。通过目标元素Pb的真实浓度与其特征谱线LIBS强度线性定量模型分析,干样样品的线性相关系数远大于鲜样样品,此时猪肉干样样品检测限为5.13 mg·kg-1,说明干样样品具有一定的预测精度。整个工作证明猪肉等农产品在经过合适的、简单的物理方法前处理后,有望在LIBS分析灵敏度和检测精度方面发挥应有的潜力,且该物理方法前处理同样适用于其他肉类的LIBS检测分析。     

Detection and quantification of heavy metal elements in gallstones using X-ray fluorescence spectrometry

Gallbladder cancer, which is associated with the heavy metal toxicity, is one of the most dangerous malignancies. High occurrence of gallstones in the gallbladder is a well-recognized risk factor for gallbladder cancer. Accumulation of heavy and toxic metals in the biliary system is one of the main causes of gallstone formation and leads to gallbladder cancer if it remains untreated. In this work, we investigate heavy and toxic metals in gallstones to identify their association as potential risk factors for gallbladder cancer. Detection and quantification of the heavy and toxic chemicals present in gallstones are important to define etiopathogenic factors that, in turn, are useful to identify preventive and therapeutic strategies. We quantified the heavy metals in gallstones collected from patients of different age groups and dietary habits. We carried out chemical composition studies of trace and heavy metal elements present in gallstones by applying Fourier transform infrared (FTIR) spectroscopy and wavelength-dispersive X-ray fluorescence (WD-XRF) spectrometry. We also compared our experimental results with the results obtained from atomic absorption spectroscopy, as well as values previously reported in literature. These findings demonstrate the potential of WD-XRF spectrometry and FTIR spectroscopy as important emerging diagnostic tools in the field of gastroenterology.     

Laser Induced Breakdown Spectroscopy for Comparative Quantitative Analysis of Betel Leaves from Pakistan

Laser induced breakdown Spectroscopy (LIBS) was applied for the elemental analysis and exposure of the heavy metals in betel leaves in air. Pulsed Nd∶YAG (1064 nm) in conjunction with a suitable detector (LIBS 2000+, Ocean Optics, Inc) having the optical resolution of 0.06 nm was used to record the emission spectra from 220 to 720 nm. Elements like Al, Ba, Ca, Cr, Cu, P, Fe, K, Mg, Mn, Na, P, S, Sr, and Zn were found to present in the samples. The relative abundances of the observed elements were calculated through standard calibration curve method, integrated intensity ratio method, and weight percentage LIBS approach. LIBS findings were validated by comparing its results with the results obtained using a typical analytical technique of Inductively Coupled plasma-optical emission spectroscopy (ICP-OES). Limit of detection (LOD) of the LIBS system was also estimated for heavy metals. The experience gain through this work implies that LIBS could be highly applicable for testing the quality and purity of food products.     

Development of a laser-induced breakdown spectroscopy method for soil and ecological analysis (review)

The application of laser spectrochemical analysis to testing for basic compounds and nutritious/toxic elements in soil has been reviewed. A combined laser-spark approach has been applied for the rapid measurement of the carbon content in soil. Spectra have been excited both directly in a laser-ablation plume and by passing a pulsed electric discharge through the plume. The emission spectrum intensity in the combined plasma is considerably higher. The application of a complex of methods to carbon determination in soil has shown that in fact the data on the humus content usually obtained in agrochemical practice by a conventional method of carbon oxidation by potassium dichromate need to be corrected taking into account the possibility of incomplete oxidation of organic matter in soil. The efficiency of various double-pulse LIBS applications has been demonstrated in solving a number of environmental problems such as the determination of heavy and toxic metals in soil and the detection of sulfur in coal. The instrumentation and analytical procedures have been proposed and optimized for rapid control of the chlorine content in plant samples. The technique can be easily extended to ecological monitoring of toxic elements and heavy metals in any biogenic material.     

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。     

基于激光诱导击穿光谱的洋葱在线原位检测

激光诱导击穿光谱(Laser-induced breakdown spectroscopy, LIBS)是一种分析多元素的光学技术,可用于新鲜蔬菜的快速检测.以洋葱为例,采用LIBS对其含有的元素进行了在线原位检测.用乙酸铅溶液污染洋葱以模拟大气湿沉降的重金属污染现象,并进行重金属Pb元素检测.使用主成分分析(principal components analysis, PCA)和反向传播人工神经网络(back-propagating artificial neutral network, BP-ANN),以洋葱、大蒜、小葱为样品进行区分检测.洋葱光谱中的特征谱线包括Si、Fe、C、Mg、Al、Ca、Ti、Sr、Ba、Na、Li和K等元素,以及N、H、O的谱线和CN分子谱带.不同浓度梯度乙酸铅溶液污染的洋葱样品中都能检测出Pb元素,其相对强度与溶液浓度成比例.此外,PCA的结果表明洋葱、小葱、大蒜的区分效果明显,BP-ANN交叉验证的识别率为89.47%.结果证明LIBS在对元素进行快速分析时具有较好的识别能力,是检测新鲜蔬菜的有效手段.     

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。     

激光诱导击穿光谱对污染鱼体内重金属元素分布与含量的分析

环境污染可造成生物体的中毒、病变及死亡。生物体各组织对污染物质的吸收、积累情况是不同的。生物体各组织对污染物质重金属元素的吸收是生物医学中的一项重要研究。采用激光诱导击穿光谱(LIBS)方法对受污染的鱼体各组织进行了重金属元素定量分析。实验中得到了一组探测鱼类组织元素成份的LIBS最佳条件,拟合了Pb和Ba元素的定标曲线并通过外标法测定了重金属含量。实验结果表明,鱼体中肝脏及口腮等部位有重金属积累,而在鱼肉中重金属含量极低。所提出的方法可用于生物体受污染影响的评估研究, 在生物医学领域有重要推广价值。     

基于不同化学计量学方法的土壤重金属激光诱导击穿光谱定量分析研究

工业的发展及城市化进程的深入,造成大量耕地土壤遭受重金属污染,土壤重金属元素的准确检测对制定土壤重金属防治决策提供有效参考。本研究应用激光诱导击穿光谱(LIBS)结合化学计量学方法对土壤中的铅(Pb)和镉(Cd)元素进行定量分析。根据土壤重金属污染的不同程度,人为制作了含有Pb和Cd元素的15个浓度梯度的土壤样本,并采集各个样本的LIBS谱线。采用剔除异常光谱和数据归一化来减少试验误差和噪声。综合土壤LIBS发射谱线中Pb和Cd元素谱峰信息以及美国国家标准与技术研究院(NIST)的标准原子光谱数据库,选取了Pb,Cd元素的分析谱线与分析谱线区间,对比分析基于多元线性回归(MLR)、偏最小二乘回归(PLSR)、最小二乘支持向量机(LS-SVM)和反向传播人工神经网络(BP-ANN)算法,建立分析谱线区间与对应Pb和Cd元素浓度之间的定量回归模型。结果表明,非线性的LS-SVM和BP-ANN的模型的预测性能优于线性MLR和PLSR模型,这可能是因为非线性模型能够通过自适应较好地解决土壤基体效应的影响。研究表明,LIBS技术结合多元化学计量学方法能够为土壤重金属准确检测提供新的分析手段,为制定农业土壤重金属防治决策提供有效的理论基础。     

激光等离子体光谱分析技术的发展现状

综述了近几年来应用激光等离子体光谱分析技术在不同领域所取得的研究成果,包括利用激光诱导击穿光谱学(LIBS)和激光诱导等离子体光谱学(LIPS)方法对固体样品(如金属合金、土壤、混凝土、矿物、化石、药品等)、液体样品(溶液、纯净水、液体喷射流等)和气体样品(大气、纯净气体、水蒸气和气溶胶等)中物质成分和相关特性的分析研究,以及在其他方面的研究应用;讨论了影响检测性能的因素,如激光波长、脉冲能量、功率密度、环境气氛、外加电场、样品表面涂层以及样品材料性能等对分析精确度和检出限的影响;对一些改进的实验装置及方法也进行了简单介绍。激光等离子体光谱分析技术的发展,为许多科学和应用研究创造了方便和快捷的有利条件,对科技进步有深远影响。     

第十五届全国原子与分子物理学术会议: 用激光诱导击穿光谱技术定量分析油漆中的有害重金属

很多轻工业产品需要用到油性油漆，其中的重金属元素的含量是否超标将会直接影响到产品质量及其安全性。因此发展轻工产品中重金属含量的快速检测技术，对促进国民经济的发展和保障消费者生命安全具有重要的意义。我们利用激光诱导击穿光谱技术实现了对油漆中有害重金属含量的快速定性和定量分析。通过观测激光等离子体中重金属原子辐射强度可以定性测量重金属含量的大体水平。然后，在相同检测条件下，将已知浓度的标准样品作为参考，制定出各元素的校正曲线，使用外标法，就能够实现定量分析。对Pb、Cr、Cd三种有害重金属元素，目前检出限分别达到9、3.5和23ppm的水平，分析相对误差小于10%，单次测量时间短于2分钟。汞的结果不太理想，检测灵敏度相对偏低，与其原子辐射寿命较短有关。我们将采取脉冲放电延长汞原子辐射弛豫时间的措施来改进汞元素的分析灵敏度，使其达到较高水平。     

用激光诱导击穿光谱技术定量分析油漆中的有害重金属

很多轻工业产品需要用到油性油漆,其中的重金属元素的含量是否超标将会直接影响到产品质量及其安全性.因此发展轻工产品中重金属含量的快速检测技术,对促进国民经济的发展和保障消费者生命安全具有重要的意义.我们利用激光诱导击穿光谱技术实现了对油漆中有害重金属含量的快速定性和定量分析.通过观测激光等离子体中重金属原子辐射强度可以定性测量重金属含量的大体水平.然后,在相同检测条件下,将已知浓度的标准样品作为参考,制定出各元素的校正曲线,使用外标法,就能够实现定量分析.对Pb、Cr、Cd三种有害重金属元素,目前检出限分别达到9、3.5和23ppm的水平,分析相对误差小于10%,单次测量时间短于2分钟.汞的结果不太理想,检测灵敏度相对偏低,与其原子辐射寿命较短有关.我们将采取脉冲放电延长汞原子辐射弛豫时间的措施来改进汞元素的分析灵敏度,使其达到较高水平.     

Identification of cholesterol gallstones using in vitro low-fluence laser-induced fluorescence spectroscopic analysis

Identifying the chemical composition of gallstones may be important in certain cases of calculus biliary disease when planning a dissolution therapy or a fragmentation of the calculi using pulsed lasers. The present study was conducted in vitro to evaluate the feasibility of distinguishing cholesterol gallstones from pigment stones. We propose an identification method in which the stone fluorescence spectrum, induced by a low fluence laser, is recorded using an optical multichannel analyser. Fluorescence spectra of twenty-two stones were recorded together with the fluorescence spectra of various pure compounds likely to compose the gallstones, using successively four different pump lasers (_p=308 nm, 337 nm, 423 nm, 469 nm). The fluorescence spectra of cholesterol gallstones are quite different from the pigment ones. Ratios of fluorescence intensities taken at three different wavelengths enable one to distinguish easily between cholesterol and pigment stones.     

石墨富集结合空间约束水体重金属LIBS检测方法研究

针对水体重金属污染检测的需求,研究了以高纯石墨片为水体富集基底,样品多次富集结合等离子体空间约束的水体重金属LIBS检测方法, 并对Pb,Cu,Cd,Ni等不同重金属元素的测量稳定性及检测限进行了分析。实验采用波长为1 064 nm的Nd∶YAG调Q激光器,分辨率为0.1 nm的光纤光谱仪分别对上述水体中重金属元素含量的特征光谱进行分光探测。结果表明,样品多次富集结合空间约束方法能够有效地提高水体重金属检测的灵敏度及稳定性并降低元素检测限,空间约束条件下特征光谱强度增强约2.5倍,光谱稳定性也得到提高,相对标准偏差由非约束情况下的11.34%降低至8.77%。对不同浓度的Pb,Cu,Cd,Ni四种重金属元素进行检测并建立定标曲线,Pb,Cu,Cd,Ni的检测限均低于国家工业废水排放标准的1/6,满足工业废水重金属的检测需求,为工业废水重金属的减排控制与超标排放预警监测提供了一种有效方法和技术支持。     

石墨富集结合空间约束水体重金属LIBS检测方法研究WT

针对水体重金属污染检测的需求,研究了以高纯石墨片为水体富集基底,样品多次富集结合等离子体空间约束的水体重金属LIBS检测方法,并对Pb,Cu,Cd,Ni等不同重金属元素的测量稳定性及检测限进行了分析.实验采用波长为1 064 nm的Nd∶YAG调Q激光器,分辨率为0.1 nm的光纤光谱仪分别对上述水体中重金属元素含量的特征光谱进行分光探测.结果表明,样品多次富集结合空间约束方法能够有效地提高水体重金属检测的灵敏度及稳定性并降低元素检测限,空间约束条件下特征光谱强度增强约2.5倍,光谱稳定性也得到提高,相对标准偏差由非约束情况下的11.34%降低至8.77%.对不同浓度的Pb,Cu,Cd,Ni四种重金属元素进行检测并建立定标曲线,Pb,Cu,Cd,Ni的检测限均低于国家工业废水排放标准的1/6,满足工业废水重金属的检测需求,为工业废水重金属的减排控制与超标排放预警监测提供了一种有效方法和技术支持.     

激光诱导击穿光谱技术在土壤元素检测中的应用

激光诱导击穿光谱(laser-induced breakdown spectroscopy,LIBS)是一种原子发射光谱,具有对样本简单(或不需要)预处理,多元素同步、远距离测量,适用性广等独特优势。因此,LIBS分析技术被看作是未来化学分析和快速绿色分析技术领域的新兴技术。目前,土壤污染(重金属、有机污染等)检测与防治已成为现代农业和农业可持续发展关注和研究的热点问题。介绍了常见LIBS系统的结构组成以及工作原理,综述了LIBS技术对土壤中大量营养元素,重金属元素和土壤相关其他物质的研究现状和主要进展,提出了LIBS检测技术在土壤元素等方面的研究方向和发展趋势。     

特征变量提取方法对脐橙皮中Cu元素LIBS检测精度的影响

食品重金属污染日趋严重,常规的实验室化学分析方法难以满足现代农业发展的需求。激光诱导击穿光谱是一种新兴的快速无损检测新方法,但该技术存在检测稳定性、灵敏度和精确度不高的瓶颈问题。本工作以江西特色水果赣南脐橙中的Cu元素为研究对象,探讨采用LIBS技术检测的可行性问题。首先对脐橙样品进行实验室污染处理,再利用优化的试验参数(激光能量120 mJ、光谱采集延迟时间1.14 μs、采集积分时间2 ms)采集样品表皮的LIBS光谱信息,然后利用AAS对激光击打部位果皮进行Cu元素真实含量检测。提取Cu Ⅰ324.7 nm与Cu Ⅰ 327.4 nm作为Cu元素定量分析特征光谱,建立Cu元素真实浓度与Cu Ⅰ 324.7强度、Cu Ⅰ 327.4强度、Cu Ⅰ 324.7与Cu Ⅰ 327.4强度之和的关系模型,并对模型的灵敏度和预测准确度进行了分析。结果显示,三个关系模型的浓度预测相对误差均在7.01%以下,最小分别达到了0.02%,0.01%和0.02%,平均相对误差分别为2.33%,3.10%和2.63%。试验表明,寻找合适的特征变量能明显提高定量分析结果的精确度。此外,该研究有助于为重金属元素在果皮果肉中的传输规律提供理论依据。     

利用激光击穿光谱检测大气中的重金属成分

大气中的重金属成分对人类健康有严重的危害,有必要对其进行检测和控制,利用自行搭建的一套激光击穿光谱大气监测系统,对煤燃烧烟气和烟花爆竹燃烧烟气污染的大气作为研究对象,通过软件进行处理,获得了大气中的多种重金属元素的L1BS光谱图。利用模拟的被Cd元素污染的大气进行了定量分析,配制含Cd不同浓度的大气样品进行了实验,得到了Cd元素的校准曲线,其线性拟合相关度为0.9938,计算得到其检出限为1mg/m~3。这些研究结果有效地促进了激光击穿光谱在大气污染物检测实用化技术方向的发展。