为了促进激光诱导击穿光谱技术在核工业领域中的应用与发展,利用飞秒激光对高纯石墨中的钍(Th)元素开展了定量分析研究。采用标准加样法制备了钍含量在0.35%~35.15%范围内的9个分析样品,以类比钍基核燃料中的钍含量。通过改变光谱采集...为了促进激光诱导击穿光谱技术在核工业领域中的应用与发展,利用飞秒激光对高纯石墨中的钍(Th)元素开展了定量分析研究。采用标准加样法制备了钍含量在0.35%~35.15%范围内的9个分析样品,以类比钍基核燃料中的钍含量。通过改变光谱采集方式、延时条件及调节飞秒激光脉冲能量对实验条件进行优化。在优化的实验条件下,对所有样品进行激发以采集等离子体光谱信息用于定量分析研究。得出以下结果:对比定点激发采集光谱结果,采用靶面连续移动式的光谱重复性好,钍原子(Th I 396.21 nm)谱线强度获得大约2倍的增强,重复测量的相对标准偏差由20.4%降至5.7%;高含量区间内钍元素谱线存在明显的自吸收效应,采用指数函数对整个含量区间与分析线(Th I 394.42 nm、396.21 nm和766.53 nm)强度进行非线性拟合,可以有效获取分析线的饱和阈值;基本定标法适用于饱和阈值以下的含量区间,分析线对较低含量的未知样品的预测分析具有较高的精确度;采用内标法(以C I 247.85 nm线为内标线),可以实现积分强度和峰值强度与整个区间含量的线性拟合,其中,基于高饱和阈值分析线(766.53 nm)的积分强度能够较好地实现高含量未知样品的含量预测。实验结果说明:飞秒激光诱导击穿光谱技术具有钍基核燃料循环过程中钍含量监测分析的潜力。展开更多
The quantitative determination of heavy metals in aquatic products is of great importance for food security issues.Laser-induced breakdown spectroscopy(LIBS)has been used in a variety of foodstuff analysis,but is stil...The quantitative determination of heavy metals in aquatic products is of great importance for food security issues.Laser-induced breakdown spectroscopy(LIBS)has been used in a variety of foodstuff analysis,but is still limited by its low sensitivity when targeting trace heavy metals.In this work,we compare three sample enrichment methods,namely drying,carbonization,and ashing,for increasing detection sensitivity by LIBS analysis for Pb and Cr in oyster samples.The results demonstrate that carbonization can remove a significant amount of the contributions of organic elements C,H,N and O;meanwhile,the signals of the metallic elements such as Cu,Pb,Sr,Ca,Cr and Mg are enhanced by3–6 times after carbonization,and further enhanced by 5–9 times after ashing.Such enhancement is not only due to the more concentrated metallic elements in the sample compared to the dried ones,but also the unifying of the matter in carbonized and ashed samples from which higher plasma temperature and electron density are observed.This condition favors the detection of trace elements.According to the calibration curves with univariate and multivariate analysis,the ashing method is considered to be the best choice.The limits of detection of the ashing method are 0.52 mg kg-1 for Pb and0.08 mg kg-1 for Cr,which can detect the presence of heavy metals in the oysters exceeding the maximum limits of Pb and Cr required by the Chinese national standard.This method provides a promising application for the heavy metal contamination monitoring in the aquatic product industry.展开更多
Laser-induced breakdown spectroscopy(LIBS)is a capable technique for elementary analysis,while LIBS quantitation is still under development.In quantitation,precise laser focusing plays an important role because it ens...Laser-induced breakdown spectroscopy(LIBS)is a capable technique for elementary analysis,while LIBS quantitation is still under development.In quantitation,precise laser focusing plays an important role because it ensures the distance between the laser and samples.In the present work,we employed spectral intensity as a direct way to assist laser focusing in LIBS quantitation for copper alloys.It is found that both the air emission and the copper line could be used to determine the position of the sample surface by referencing the intensity maximum.Nevertheless,the fine quantitation was only realized at the position where the air emission(e.g.O(I)777.4 nm)reached intensity maximum,and also in this way,a repeatable quantitation was successfully achieved even after 120 days.The results suggested that the LIBS quantitation was highly dependent on the focusing position of the laser,and spectra-assisted focusing could be a simple way to find the identical condition for different samples’detection.In the future,this method might be applicable in field measurements for LIBS analysis of solids.展开更多
文摘为了促进激光诱导击穿光谱技术在核工业领域中的应用与发展,利用飞秒激光对高纯石墨中的钍(Th)元素开展了定量分析研究。采用标准加样法制备了钍含量在0.35%~35.15%范围内的9个分析样品,以类比钍基核燃料中的钍含量。通过改变光谱采集方式、延时条件及调节飞秒激光脉冲能量对实验条件进行优化。在优化的实验条件下,对所有样品进行激发以采集等离子体光谱信息用于定量分析研究。得出以下结果:对比定点激发采集光谱结果,采用靶面连续移动式的光谱重复性好,钍原子(Th I 396.21 nm)谱线强度获得大约2倍的增强,重复测量的相对标准偏差由20.4%降至5.7%;高含量区间内钍元素谱线存在明显的自吸收效应,采用指数函数对整个含量区间与分析线(Th I 394.42 nm、396.21 nm和766.53 nm)强度进行非线性拟合,可以有效获取分析线的饱和阈值;基本定标法适用于饱和阈值以下的含量区间,分析线对较低含量的未知样品的预测分析具有较高的精确度;采用内标法(以C I 247.85 nm线为内标线),可以实现积分强度和峰值强度与整个区间含量的线性拟合,其中,基于高饱和阈值分析线(766.53 nm)的积分强度能够较好地实现高含量未知样品的含量预测。实验结果说明:飞秒激光诱导击穿光谱技术具有钍基核燃料循环过程中钍含量监测分析的潜力。
基金supported by the National Key Research and Development Program of China(No.2019YFD0901701)National Natural Science Foundation of China(Nos.12174359and 61975190)Provincial Key Research and Development Program of Shandong,China(No.2019GHZ010)。
文摘The quantitative determination of heavy metals in aquatic products is of great importance for food security issues.Laser-induced breakdown spectroscopy(LIBS)has been used in a variety of foodstuff analysis,but is still limited by its low sensitivity when targeting trace heavy metals.In this work,we compare three sample enrichment methods,namely drying,carbonization,and ashing,for increasing detection sensitivity by LIBS analysis for Pb and Cr in oyster samples.The results demonstrate that carbonization can remove a significant amount of the contributions of organic elements C,H,N and O;meanwhile,the signals of the metallic elements such as Cu,Pb,Sr,Ca,Cr and Mg are enhanced by3–6 times after carbonization,and further enhanced by 5–9 times after ashing.Such enhancement is not only due to the more concentrated metallic elements in the sample compared to the dried ones,but also the unifying of the matter in carbonized and ashed samples from which higher plasma temperature and electron density are observed.This condition favors the detection of trace elements.According to the calibration curves with univariate and multivariate analysis,the ashing method is considered to be the best choice.The limits of detection of the ashing method are 0.52 mg kg-1 for Pb and0.08 mg kg-1 for Cr,which can detect the presence of heavy metals in the oysters exceeding the maximum limits of Pb and Cr required by the Chinese national standard.This method provides a promising application for the heavy metal contamination monitoring in the aquatic product industry.
基金financially supported by the Provincial Key Research and Development Program of Shandong,China(No.2019GHZ010)the Natural Science Foundation of Shandong Province(No.ZR2020MF123)+1 种基金National Natural Science Foundation of China(Nos.61975190 and12174359)the Fundamental Research Funds for the Central Universities(No.202161002)。
文摘Laser-induced breakdown spectroscopy(LIBS)is a capable technique for elementary analysis,while LIBS quantitation is still under development.In quantitation,precise laser focusing plays an important role because it ensures the distance between the laser and samples.In the present work,we employed spectral intensity as a direct way to assist laser focusing in LIBS quantitation for copper alloys.It is found that both the air emission and the copper line could be used to determine the position of the sample surface by referencing the intensity maximum.Nevertheless,the fine quantitation was only realized at the position where the air emission(e.g.O(I)777.4 nm)reached intensity maximum,and also in this way,a repeatable quantitation was successfully achieved even after 120 days.The results suggested that the LIBS quantitation was highly dependent on the focusing position of the laser,and spectra-assisted focusing could be a simple way to find the identical condition for different samples’detection.In the future,this method might be applicable in field measurements for LIBS analysis of solids.
