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。     

基于飞秒激光等离子体丝诱导击穿光谱探测土壤重金属Cr元素含量

本文基于飞秒激光等离子体丝诱导击穿光谱对土壤重金属Cr元素含量进行了实验研究.利用荧光法对等离子体丝的长度进行测量,给出了在不同焦距聚焦透镜作用下土壤中Cr425.5 nm的谱线强度空间分布,实验给出了Cr元素的定标曲线.实验结果表明,土壤中Cr元素浓度分析测量的相对标准偏差小于5%,土壤中重金属Cr元素的检测极限为7.85 ppm.表明飞秒激光等离子体丝诱导击穿光谱技术在土壤重金属Cr元素含量的定量探测方面是完全可行的.     

激光诱导击穿光谱对四种香的快速检测

激光诱导击穿光谱技术(laser-induced breakdown spectroscopy)作为一种极具前景的分析和测量技术应用日益广泛。对四种香(艾草香、藏香、檀香、沉香)样品进行了激光等离子体光谱测量和分析, 得到了样品中元素的成分；并且对四种香样品中的Cu，Mn，Ca和Fe四种金属元素典型谱线的强度进行了统计分析和元素含量的对比。基于等离子体的局域热动力学的平衡模型, 计算了Ca元素的等离子体温度。实验结果为采用激光诱导击穿光谱对香品成分进行快速检测和分析的可行性提供了依据。     

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.     

基于发射光谱及成分分析的激光除漆机理研究

基于激光诱导击穿光谱和X射线能谱技术,测量了激光与油漆作用时发射光谱及作用前后元素成分的变化,以此研究了激光除漆的机理。实验测量了不同纳秒激光能量下激光诱导击穿油漆表面的光谱,计算了等离子体的电子密度和温度。通过扫描电子显微镜对油漆烧蚀形貌进行了分析,采用X射线能谱仪测量了烧蚀前后油漆成分的变化。研究结果表明,等离子体电子密度、温度以及烧蚀区域大小都随着入射激光能量的增加逐渐增加。在激光作用前后油漆中碳(C)含量明显降低,原子百分比从78.25%降低到67.07%,说明激光与油漆作用过程中发生了烧蚀。通过对比钛(Ti)元素、C元素和铝(Al)元素的相对原子比例,表明更高的激光能量下油漆烧蚀的更剧烈。该工作对深入研究激光除漆机理有重要意义。     

杨树叶片的飞秒等离子体丝诱导击穿光谱研究

开展了杨树叶片的飞秒激光等离子体丝诱导击穿光谱研究, 定性比较分析了长春市区的第一汽车厂、火车站、净月潭公园及长春理工大学四个地理区域的杨树叶片中重金属元素Ca, Fe和Cr. 实验结果表明, 通过分析杨树叶片中Ca Ⅱ 393.37 nm和Fe Ⅰ 422.87 nm光谱谱线可知叶茎中Ca和Fe元素浓度均高于叶肉. 比较长春四个地理区域的杨树叶的飞秒激光等离子体丝诱导击穿光谱, 发现汽车厂附近的杨树叶内重金属Ca, Fe和Cr 元素浓度最高, 净月公园的杨树叶重金属浓度最低. 由于飞秒激光等离子体丝光强度的“光学钳箍”效应, 对于杨树叶片这种表面不平整样品, 仍可获得稳定性较好的等离子体光谱. 飞秒激光等离子体丝诱导光谱技术有望在环境污染在线检测具有广泛的潜在应用.     

用高重频激光剥离-火花诱导击穿光谱分析铝合金样品

为了提高基于等离子体原子发射光谱元素分析技术的分析速度，在高重复频率的前提下建立了一套激光剥离-火花诱导击穿光谱元素分析系统并以铝合金为样品开展了光谱分析。实验以低脉冲能量的声光调Q固体激光脉冲剥离样品，并触发高压火花放电以增强等离子体辐射、提高光谱分析灵敏度。研究结果表明： 在高重频火花放电的作用下，等离子体辐射的峰值强度和弛豫时间分别得到了增强和延长，信号的时间积分强度增强因子可以达到1～2个数量级，且更易于实现时间分辨的信号检测。对铝合金中微量铬元素分析的检出限可达~132 ppm。该研究验证了高重频激光剥离-火花诱导击穿光谱用于分析固体样品元素的可行性，其技术有望在固体样品元素的快速分析中发挥一定的作用。该光谱技术能同时兼顾扫描成像的速度、空间分辨率和光谱分析灵敏度，并为固体样品的二维或者三维元素分布的高分辨快速扫描成像分析提供了一种很好的技术途径。     

基于激光诱导击穿光谱技术定量分析食用明胶中的铬元素

利用激光诱导击穿光谱技术对食用明胶样品中的铬元素进行定量分析.采用Nd:YAG脉冲激光器三倍频输出的355 nm激光诱导击穿食用明胶产生激光等离子体,测量等离子发射光谱.实验数据表明:使用内标法定量分析食用明胶样品中铬元素浓度分别为10—200 ppm(1 ppm=10-6)时,铬元素含量与分析谱线(CrI:245.43 nm)强度之间具有很好的线性关系.分析了光谱探测延迟时间对明胶中铬元素激光诱导击穿光谱的影响,利用信号强度与信噪比获得了优化的光谱探测延迟时间实验参数.     

激光诱导击穿光谱应用于三种水果样品微量元素的分析

激光诱导击穿光谱(LIBS)在植物样品上面的应用是一个较新的课题. 为将LIBS技术能实际应用于与食品安全相关的领域，实验中对三种真空冻干水果样品进行了初步LIBS实验研究，鉴别了其LIBS光谱，并选取典型光谱线，运用统计学方法分析比较了三种水果中Ca，Na，K，Fe，Al，Mg六种元素含量的差别. 实验结果表明，苹果中Na的含量最高，Ca的含量最低，三种水果样品中的K，Fe，Mg等元素含量也都有差异. 实验结果还表明LIBS技术是一种检测、对比植物样品中微量元素含量的有效手段. 关键词： 激光诱导击穿光谱 等离子体 植物样品 微量元素     

水中铅元素的激光诱导击穿光谱-激光诱导荧光超灵敏检测

为了实现对水中有害重金属元素铅的超灵敏快速检测,保证饮用水源的安全,对激光诱导击穿光谱(LIBS)-激光诱导荧光(LIF)联用技术进行研究;采用木片吸水将液体样品分析转换为固体样品分析,消除了采用LIBS技术直接分析水样品时水对原子辐射以及光学收光系统的影响;采用一束可调谐染料激光共振激发激光等离子体中的铅原子,探测其LIF以大幅提高光谱分析的灵敏度;在优化的实验条件下得到水中铅的校正曲线。结果表明,在当前实验条件下铅的检出限可达到3.2×10-9,LIBS-LIF联用技术结合木片吸水法可以直接应用于水环境中痕量铅元素的超灵敏快速检测,从而可监控有害重金属造成的水源污染。     

Compact spectral software/hardware system based on an SL-13 steeloscope

We have designed a compact spectral software/hardware system based on an SL-13 steeloscope for rapid quantitative atomic emission spectral analysis of the elemental composition of metals and alloys, products of the paint and varnish industry, monitoring the content of toxic elements (heavy metals) in food products, specimens of biological and plant origin, soils and waters, with computer processing of the analysis results. We demonstrate the prospects for upgrading similar steeloscopes and steelometers in plants of the Republic of Belarus, with the aim of improving the quality of analyses and reducing their cost. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 411–414, May–June, 2006.     

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。     

ICP-AES测定碘海醇中的19种金属杂质

建立电感耦合等离子体-原子发射光谱法测定碘海醇中19种金属杂质的方法。为克服各元素之间的光谱干扰,同时保证检测灵敏度,将所有元素分为3个系统,确定合适的发射谱线和观测模式,优化等离子参数。在一定的浓度范围内,各元素谱线的发射强度与浓度均呈良好的线性关系,相关系数均大于0.9992,加标回收率为90.5%—110.7%,检出限均满足测定要求。该方法专属性好、灵敏度高、准确、快捷,可作为一种通用方法用于化学原料药中金属杂质的测定,以替代传统的重金属检查法。     

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.     

Optimum spectral window for imaging of art with optical coherence tomography

Optical coherence tomography (OCT) has been shown to have potential for important applications in the field of art conservation and archaeology due to its ability to image subsurface microstructures non-invasively. However, its depth of penetration in painted objects is limited due to the strong scattering properties of artists’ paints. VIS–NIR (400–2,400 nm) reflectance spectra of a wide variety of paints made with historic artists’ pigments have been measured. The best spectral window with which to use OCT for the imaging of subsurface structure of paintings was found to be around 2.2 μm. The same spectral window would also be most suitable for direct infrared imaging of preparatory sketches under the paint layers. The reflectance spectra from a large sample of chemically verified pigments provide information on the spectral transparency of historic artists’ pigments/paints as well as a reference set of spectra for pigment identification. The results of the paper suggest that broadband sources at ~2 μm are highly desirable for OCT applications in art and potentially material science in general.     

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.     

用ICP-AES方法测定淀粉中铅、砷的含量

采用ICP-AES(电感耦合等离子体发射光谱)法,以硝酸镍作为基体改进剂,对淀粉中的铅、砷含量进行了测定;探讨了样品灰化方法及灰化原子化温度、基体改进剂对测定结果的影响.实验结果表明,用ICP-AES方法测定淀粉样品中铅、砷一类有害重金属含量,数据、结果的重现性好,方法简便易行、测定结果准确.     

Raman spectroscopy of automotive paints: Forensic analysis of variability and spectral quality

Raman spectroscopy was evaluated as a forensic technique for the analysis of automotive paints with the purpose to verify the measurement variability as well as to study the spectral quality by means of parameters and conditions. The objective lens, accumulation number, and laser (power, mode, and wavelength) were observed to significantly affect the spectral quality and thus should be taken into consideration during the development of a forensic database. On the other hand, exposure time, Raman shift range, and baseline correction had less influence on the features of the obtained spectra. Interestingly, samples collected from the bumper coating composed of a plastic substrate in comparison with fragments obtained from other parts of the same vehicle containing metallic substrate showed different absorption band patterns. In addition, less variability of data acquired directly onto the paint chip’s surface has demonstrated that direct analysis should be preferred during spectra library development as opposed to cross-section measurements. Sample homogeneity and distinction power of the technique combined with Principal Components Analysis were also investigated. The preliminary results showed that although Raman spectroscopy is extremely accurate in the identification of vehicles, it is necessary to pay particular attention to the spectral variability in order to avoid false database matching and misleading of forensic investigations. Therefore, we suggest that separated spectra library shall be developed for each laser wavelength as well as for each sample substrate. Further studies with a higher number of paint chips will enable the establishment of prediction models aimed to identify unknown samples involved in hit-and-run cases.