用于液相样品中痕量金属元素探测的基底辅助LIBS方法研究
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摘要
激光诱导击穿光谱(Laser Induced Breakdown Spectroscopy,简称LIBS)是基于高功率脉冲激光与物质相互作用产生瞬态等离子体，通过分析等离子体发射光谱中原子、离子的特征谱线，实现对待测物质定性与定量分析的一种光谱技术。LIBS作为一项新兴的化学成分分析技术，因其具有快速响应、无需样品预处理、多元素同时分析以及可用于现场实时、无接触原位探测等优势，已经被广泛应用到各个领域，并取得了不同程度的成功。然而LIBS对液相样品检测时，由于等离子体受到液体内部压力、波动、吸收以及溅射等因素的影响，其寿命与空气中相比大大缩短，相应的探测灵敏度也明显降低。本论文针对液相样品中的痕量金属元素探测灵敏度低的问题，发展了两种基底辅助LIBS的增强方法，即滤纸富集辅助和铝靶基底间接烧蚀辅助LIBS方法，以期达到LIBS对液相样品中金属元素痕量探测的目的，主要的研究工作如下。
针对水溶液中痕量重金属探测，发展了以滤纸富集辅助的LIBS方法。该方法是将溶液滴到滤纸基底表面，滤纸基底一方面改变激发环境，提高烧蚀效果，同时伴随着一定的水分浸湿和蒸发以实现取样富集，从而改善了取样效果乃至探测灵敏度。应用该方法实现了水中Mn、Cu、Cd、Cr、Pb及Zn重金属元素的增强探测，相比对液体样品直接探测时，检测限降低了十几倍，基本达到了国家污水中重金属元素允许排放浓度的检测标准。同时，为了评估该方法应用到水体中的多种重金属元素进行同时探测时基体效应的影响，利用该方法对混合水溶液中Cd、Cr、Cu、Mn元素同时进行了探测，得出基体效应对不同元素的定标曲线和探测极限产生了不同程度的影响，但是对于探测的准确度影响较小，使得探测值与实际值之间的误差在5%左右，探测值处于一定的置信区间内。并且该方法也应用到更复杂水体海水溶液中的Mn的探测，获得了定量分析结果。结果表明，滤纸富集辅助LIBS增强方法可望发展成一种应用到水体环境中痕量重金属元素探测的有效方法。
针对相对于水溶液较为难探测粘稠性油样品中的痕量金属元素，论文作者在法国里昂第一大学访学期内，发展了以铝靶为基底的间接烧蚀的LIBS增强方法，从方法的物理机制到增强探测的应用开展了系列的工作。实验中将粘稠性油样品均匀的涂抹在铝靶基底的表面，形成一层大约15微米的油膜，激光聚焦在铝靶上产生的高温等离子体继而间接烧蚀油膜，因此将该增强方法命名为铝靶基底辅助的间接烧蚀LIBS方法。所获得的等离子体元素辐射、特征参数以及成像的时空分辨演化特性分析，表明在等离子体扩展的前期，油膜将会对等离子体的扩展有一定的限制作用，随着延时的增加，限制作用逐渐消失，正是金属等离子体与油膜相互作用之后，在其外围形成一个等离子体温度相对较高的区域（大约15000K），相当于对冷却的等离子体二次激发，延长了等离子体的寿命。在了解了间接烧蚀诱导的等离子体的物理演化过程的基础上，确定了探测油膜中元素最强辐射的空间位置即等离子体距离铝靶表面2mm和演化的时间即探测延时2μs。
为了评估间接烧蚀辅助LIBS的增强能力，利用得到的最佳探测条件，该方法对机油中的磨损金属元素的进行了探测。选取含有12种痕量磨损金属元素的标准机油为样品，确定每种元素最佳的分析谱线，绘制了相应的定标曲线并计算了每种元素的探测限，结果显示在机油中，镁、铜和银的探测限达到了ppm量级以下，其他元素的探测限也在几个ppm量级，与用滤纸分析机油的结果相比，探测限都有了不同的程度的改善，甚至优于其双脉冲LIBS探测的结果。论文还对油样品中所含的多种痕量金属元素进行了同时的探测，获得了相应的定标曲线，同时选取完全不同的油种为样品，对不同油种中基体效应的影响进行了评估，得到铝靶为基底的间接烧蚀LIBS方法在应用到不同油种中金属元素的探测时，其之间的基体效应对最终的定量分析结果影响较弱，几乎可以忽略。结果表明铝靶基底间接烧蚀辅助LIBS方法可望成为一种探测粘稠性液体中痕量金属元素的有效方法。
本论文对以上的研究工作的基础上，还对滤纸富集辅助LIBS和铝靶基底间接烧蚀辅助LIBS这两种方法的应用进行了展望，对如何提高探测方法的稳定性和适应性是以后努力工作的方向。并在有关铝靶基底间接烧蚀辅助LIBS方法研究中，鉴别间接烧蚀产生的等离子体与击穿铝靶产生的等离子体的深入研究的方案未能实施，这是本论文的一个遗憾，期望在未来的工作中可进一步的研究。
Laser-induced breakdown spectroscopy (LIBS) is a newly developed technique forelement analysis. It is based on the analysis of spectral emission from laser inducedplasma produced by the ablation of investigated substance with a high power laser pulse.LIBS has drawn growing attention in the past tens of years as a rapid, on-line, sensitive,and multi-elements analysis method with no or little sample preparation. It has beenextensively used for a wide range of scientific and industrial applications with differentdegrees of success. However, due to complex process of the ablation in bulk, the lifetimeof plasma is relatively short which result in poor detection sensitivity compared with thatin air. In this thesis, in order to improve the detection sensitivity of trace metal elementsin liquid samples, two enhanced approaches named substrate-assisted LIBS weredeveloped.
Paper enrichment assisted LIBS was developed for detection of heavy metals in aqueoussolutions. As aqueous solutions were dipped into paper substrate, the ablation conditionwas improved, avoiding the adverse factors for the direct detection of liquid samples. Thewater was then evaporated from the substrate, so the sampling and detection sensitivitywere improved by the enrichment effect of paper substrate. Sub-ppm detection of heavymetal elements in aqueous solutions was obtained using this approach. Limits of detection(LODs) of almost elements were down to the highest concentration of each element inwastewater discharged according to the national standards. In order to evaluate the matrixeffect existed in mixed solution of many metals, this approach was also used to detectsimultaneously heavy metal elements in aqueous solutions. The results showed that thecalibration curve and limit of detection were affected for each element by matrix effect.However, the measured concentration of heavy metal elements in mixed solutions had agood agreement to the real value and the relative error was about5%, which exhibitedgood measurement accuracy of this approach. The approach was also used to detect Mn inseawater solution and calibration curve was plotted. All results indicated that the paperenrichment assisted LIBS was expected as a feasible approach for the detection of heavymetal elements in aqueous solutions.
Aluminum substrate assisted indirect ablation LIBS was developed for detection of trace metal elements in viscous liquids, which was achieved in Lyon1University. In this thesis,the physics mechanism of this approach was first investigated, and the enhanced detectionwas then achieved. In experiment, oil samples prepared was smeared with the help of aglass slide as uniformly as possible on the polished surface of an aluminum target to forma uniform thin layer with the thickness of the layer as about15μm. A laser pulse isfocused slightly under the surface of the target which induces a hot aluminum plasma.The interaction between the aluminum plasma and the layer leads to an indirectbreakdown of the oil layer, which was therefore named as aluminum substrate assistedindirect ablation LIBS. After the evolution of the plasma, one gets a mixture of thealuminum plamsa and the layer plamsa with very high temperature (about15000K) forthe sensitive detection of elements contained in the oil layer. As temporal and spatialdynamics of plasma induced by this approach were investiated, we had obtained thesensitive detection of elements from the oil layer with a detection delay of2μs and a fiberposition of2mm above the target surface.
In order to evaluate the enhancement effect of this approach, this approach was used forthe detection of wear metals in engine oils and the calibration curves were plotted. Thestandard engine oils were prepared, including12trace wear metallic elements. Weobtained the analytical line of each element and the corresponding calibration curves. Theresults showed that the LODs for wear metals in engine oils were in the several ppmlevels. Especially, the LODs for the3elements (Mg, Cu and Ag) are determined lowerthan μg/g, i.e. in the sub-ppm level. Comparison with the previously published datashowed moreover the efficiency of the introduced ablation configuration as one of themost suitable methods for highly sensitive and precise wear metal analysis in oils.Furthermore, the matrix effect induced in different oils was investigated. It suggested thatthe analytical results were hardly affected by matrix effect among different oils. Allresults indicated that aluminum substrate assisted indirect ablation LIBS was expected asa feasible approach for the detection of trace metallic elements in viscous liquids.
Besides, in this thesis, both approaches of paper enrichment assisted LIBS and aluminumsubstrate indirect ablation assisted LIBS are also discussed on how to improve thestability and flexibility for the application. For aluminum substrate indirect ablationassisted LIBS, the indirect ablation plasma produced with aluminum substrate is notimplemented, which is a pity, and will be done in further research work.
针对水溶液中痕量重金属探测，发展了以滤纸富集辅助的LIBS方法。该方法是将溶液滴到滤纸基底表面，滤纸基底一方面改变激发环境，提高烧蚀效果，同时伴随着一定的水分浸湿和蒸发以实现取样富集，从而改善了取样效果乃至探测灵敏度。应用该方法实现了水中Mn、Cu、Cd、Cr、Pb及Zn重金属元素的增强探测，相比对液体样品直接探测时，检测限降低了十几倍，基本达到了国家污水中重金属元素允许排放浓度的检测标准。同时，为了评估该方法应用到水体中的多种重金属元素进行同时探测时基体效应的影响，利用该方法对混合水溶液中Cd、Cr、Cu、Mn元素同时进行了探测，得出基体效应对不同元素的定标曲线和探测极限产生了不同程度的影响，但是对于探测的准确度影响较小，使得探测值与实际值之间的误差在5%左右，探测值处于一定的置信区间内。并且该方法也应用到更复杂水体海水溶液中的Mn的探测，获得了定量分析结果。结果表明，滤纸富集辅助LIBS增强方法可望发展成一种应用到水体环境中痕量重金属元素探测的有效方法。
针对相对于水溶液较为难探测粘稠性油样品中的痕量金属元素，论文作者在法国里昂第一大学访学期内，发展了以铝靶为基底的间接烧蚀的LIBS增强方法，从方法的物理机制到增强探测的应用开展了系列的工作。实验中将粘稠性油样品均匀的涂抹在铝靶基底的表面，形成一层大约15微米的油膜，激光聚焦在铝靶上产生的高温等离子体继而间接烧蚀油膜，因此将该增强方法命名为铝靶基底辅助的间接烧蚀LIBS方法。所获得的等离子体元素辐射、特征参数以及成像的时空分辨演化特性分析，表明在等离子体扩展的前期，油膜将会对等离子体的扩展有一定的限制作用，随着延时的增加，限制作用逐渐消失，正是金属等离子体与油膜相互作用之后，在其外围形成一个等离子体温度相对较高的区域（大约15000K），相当于对冷却的等离子体二次激发，延长了等离子体的寿命。在了解了间接烧蚀诱导的等离子体的物理演化过程的基础上，确定了探测油膜中元素最强辐射的空间位置即等离子体距离铝靶表面2mm和演化的时间即探测延时2μs。
为了评估间接烧蚀辅助LIBS的增强能力，利用得到的最佳探测条件，该方法对机油中的磨损金属元素的进行了探测。选取含有12种痕量磨损金属元素的标准机油为样品，确定每种元素最佳的分析谱线，绘制了相应的定标曲线并计算了每种元素的探测限，结果显示在机油中，镁、铜和银的探测限达到了ppm量级以下，其他元素的探测限也在几个ppm量级，与用滤纸分析机油的结果相比，探测限都有了不同的程度的改善，甚至优于其双脉冲LIBS探测的结果。论文还对油样品中所含的多种痕量金属元素进行了同时的探测，获得了相应的定标曲线，同时选取完全不同的油种为样品，对不同油种中基体效应的影响进行了评估，得到铝靶为基底的间接烧蚀LIBS方法在应用到不同油种中金属元素的探测时，其之间的基体效应对最终的定量分析结果影响较弱，几乎可以忽略。结果表明铝靶基底间接烧蚀辅助LIBS方法可望成为一种探测粘稠性液体中痕量金属元素的有效方法。
本论文对以上的研究工作的基础上，还对滤纸富集辅助LIBS和铝靶基底间接烧蚀辅助LIBS这两种方法的应用进行了展望，对如何提高探测方法的稳定性和适应性是以后努力工作的方向。并在有关铝靶基底间接烧蚀辅助LIBS方法研究中，鉴别间接烧蚀产生的等离子体与击穿铝靶产生的等离子体的深入研究的方案未能实施，这是本论文的一个遗憾，期望在未来的工作中可进一步的研究。
Laser-induced breakdown spectroscopy (LIBS) is a newly developed technique forelement analysis. It is based on the analysis of spectral emission from laser inducedplasma produced by the ablation of investigated substance with a high power laser pulse.LIBS has drawn growing attention in the past tens of years as a rapid, on-line, sensitive,and multi-elements analysis method with no or little sample preparation. It has beenextensively used for a wide range of scientific and industrial applications with differentdegrees of success. However, due to complex process of the ablation in bulk, the lifetimeof plasma is relatively short which result in poor detection sensitivity compared with thatin air. In this thesis, in order to improve the detection sensitivity of trace metal elementsin liquid samples, two enhanced approaches named substrate-assisted LIBS weredeveloped.
Paper enrichment assisted LIBS was developed for detection of heavy metals in aqueoussolutions. As aqueous solutions were dipped into paper substrate, the ablation conditionwas improved, avoiding the adverse factors for the direct detection of liquid samples. Thewater was then evaporated from the substrate, so the sampling and detection sensitivitywere improved by the enrichment effect of paper substrate. Sub-ppm detection of heavymetal elements in aqueous solutions was obtained using this approach. Limits of detection(LODs) of almost elements were down to the highest concentration of each element inwastewater discharged according to the national standards. In order to evaluate the matrixeffect existed in mixed solution of many metals, this approach was also used to detectsimultaneously heavy metal elements in aqueous solutions. The results showed that thecalibration curve and limit of detection were affected for each element by matrix effect.However, the measured concentration of heavy metal elements in mixed solutions had agood agreement to the real value and the relative error was about5%, which exhibitedgood measurement accuracy of this approach. The approach was also used to detect Mn inseawater solution and calibration curve was plotted. All results indicated that the paperenrichment assisted LIBS was expected as a feasible approach for the detection of heavymetal elements in aqueous solutions.
Aluminum substrate assisted indirect ablation LIBS was developed for detection of trace metal elements in viscous liquids, which was achieved in Lyon1University. In this thesis,the physics mechanism of this approach was first investigated, and the enhanced detectionwas then achieved. In experiment, oil samples prepared was smeared with the help of aglass slide as uniformly as possible on the polished surface of an aluminum target to forma uniform thin layer with the thickness of the layer as about15μm. A laser pulse isfocused slightly under the surface of the target which induces a hot aluminum plasma.The interaction between the aluminum plasma and the layer leads to an indirectbreakdown of the oil layer, which was therefore named as aluminum substrate assistedindirect ablation LIBS. After the evolution of the plasma, one gets a mixture of thealuminum plamsa and the layer plamsa with very high temperature (about15000K) forthe sensitive detection of elements contained in the oil layer. As temporal and spatialdynamics of plasma induced by this approach were investiated, we had obtained thesensitive detection of elements from the oil layer with a detection delay of2μs and a fiberposition of2mm above the target surface.
In order to evaluate the enhancement effect of this approach, this approach was used forthe detection of wear metals in engine oils and the calibration curves were plotted. Thestandard engine oils were prepared, including12trace wear metallic elements. Weobtained the analytical line of each element and the corresponding calibration curves. Theresults showed that the LODs for wear metals in engine oils were in the several ppmlevels. Especially, the LODs for the3elements (Mg, Cu and Ag) are determined lowerthan μg/g, i.e. in the sub-ppm level. Comparison with the previously published datashowed moreover the efficiency of the introduced ablation configuration as one of themost suitable methods for highly sensitive and precise wear metal analysis in oils.Furthermore, the matrix effect induced in different oils was investigated. It suggested thatthe analytical results were hardly affected by matrix effect among different oils. Allresults indicated that aluminum substrate assisted indirect ablation LIBS was expected asa feasible approach for the detection of trace metallic elements in viscous liquids.
Besides, in this thesis, both approaches of paper enrichment assisted LIBS and aluminumsubstrate indirect ablation assisted LIBS are also discussed on how to improve thestability and flexibility for the application. For aluminum substrate indirect ablationassisted LIBS, the indirect ablation plasma produced with aluminum substrate is notimplemented, which is a pity, and will be done in further research work.
引文
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