Determination of rare earth elements in liquid-phase samples by superhydrophobic array-assisted spark-discharge LIBS
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摘要:
快速测定液相样品中的稀土元素（REEs）对离子吸附型稀土资源勘探与开发、萃取过程质量控制、稀土资源循环利用以及核工业废水监测等领域具有重要意义。为了降低金宝搏188软件怎么用 诱导击穿光谱（LIBS）对液体样品中REEs的检出限，本研究采用超疏水阵列辅助电火花增强金宝搏188软件怎么用 诱导击穿光谱法（SHA-SD-LIBS）测定液相样品中的REEs。选择最佳的实验条件，以La II 394.91 nm、Er 402.051 nm、Ce II 418.66 nm、Nd II 424.738 nm、Gd II 443.063 nm和Pr 492.46 nm作为特征谱线，对6种不同浓度的稀土元素（La、Er、Ce、Nd、Gd、Pr）溶液建立标定曲线进行定量分析。结果表明，各标定曲线拟合系数R²均达到0.99以上，相应的检出限分别为0.007 μg/mL、0.045 μg/mL、0.011 μg/mL、0.019 μg/mL、0.041 μg/mL和0.008 μg/mL。与常规LIBS方法相比，提出的方法可以在制样简单、低成本的前提下显著降低液相样品REEs的检出限。可为快速、准确测出液相样品中的稀土元素种类、含量提供新思路。
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关键词:
- 金宝搏188软件怎么用 诱导击穿光谱 (LIBS) /
- 稀土元素 (REEs) /
- 电火花 /
- 超疏水 /
- 液相样品
Abstract:Rapid determination of rare earth elements (REEs) in liquid-phase samples is of great significance in the fields of ion-adsorption rare earth resource exploration and exploitation, quality control of extraction processes, recycling of rare earth resources, and nuclear industry wastewater monitoring. In order to reduce the detection limit of REEs in liquid samples by laser-induced breakdown spectroscopy (LIBS), superhydrophobic array-assisted spark-enhanced laser-induced breakdown spectroscopy (SHA-SD-LIBS) was used in this study to determine the REEs in liquid-phase samples. Optimal experimental conditions were chosen to measure the REEs with the parameters of La II 394.91 nm, Er 402.051 nm, Ce II 418.66 nm, Nd II 424.738 nm, Gd II 443.063 nm, and Pr 492.46 nm as the characteristic spectral lines, and the calibration curves were established for the quantitative analysis of the solutions of six rare earth elements (La, Er, Ce, Nd, Gd and Pr) with different concentrations. The results show that the fit coefficients R² of the calibration curves were above 0.99. The corresponding detection limits were 0.007 μg/mL, 0.045 μg/mL, 0.011 μg/mL, 0.019 μg/mL, 0.041 μg/mL, and 0.008 μg/mL. The proposed method is a simple, low-cost, and highly efficient way to improve the quality of the liquid-phase sample. Compared with the conventional LIBS method, the proposed method can significantly reduce the detection limit of REEs in liquid phase samples with simple sample preparation and low cost. It can serve as a basis for new rapid and accurate methods of measuring rare earth element types and contents in liquid phase samples.
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图 2 采用超疏水阵列和电火花结合增强的典型的稀土LIBS光谱
Figure 2. Typical rare-earth LIBS spectra enhanced using a combination of superhydrophobic arrays and spark-discharge
图 3 （a）超疏水阵列衬底制备及实验过程；（b）液相稀土在超疏水阵列上的亲水区域浓缩过程和接触角；（c）载玻片（上）和超疏水阵列（下）下液相稀土液滴和烘干后的富集区域
Figure 3. (a) Superhydrophobic array substrate preparation and experimental process (b) Concentration process and contact angle of hydrophilic regions of liquid-phase rare earths on superhydrophobic arrays (c) Liquid-phase rare earth droplets and enriched regions after drying under slides (top) and superhydrophobic arrays (bottom)
图 4 使用载玻片和SHA衬底下的光谱强度（a）和RSD（b）
Figure 4. Spectral intensities (a) and RSD (b) using slides and SHA substrate
图 5 使用SHA-LIBS和SHA-SD-LIBS下的光谱强度（a）和RSD（b）
Figure 5. Spectral intensity (a) and RSD (b) under the use of SHA-LIBS and SHA-SD-LIBS
图 6 载玻片、SHA-LIBS和SHA-SD-LIBS下的6种稀土元素(La、Er、Ce、Nd、Gd、Pr)的校正曲线，误差条反映了10个光谱的标准偏差。
Figure 6. Calibration curves for six rare earth elements (La, Er, Ce, Nd, Gd, Pr) under slide, SHA-LIBS, and SHA-SD-LIBS, with error bars reflecting the standard deviation of 10 spectra.
表 1 各稀土元素在标准溶液中的浓度(μg/mL)
Table 1. Concentration of each rare earth element in standard solution (μg/mL)
Sample No. La Er Ce Nd Gd Pr 1 0.1 1.5 0.6 0.75 1.0 0.1 2 0.2 2 0.7 1.0 1.5 0.2 3 0.3 2.5 0.8 1.25 2 0.3 4 0.4 3 0.9 1.5 2.5 0.4 5 0.5 3.5 1.0 1.75 3 0.5 6 0.6 4 1.1 2 3.5 0.6 
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表 2 采用不方法测定稀土元素的平均相对标准偏差(ARSD)和检出限(LOD)
Table 2. Mean relative standard deviation (ARSD) and limit of detection (LOD) of rare earth elements determined using different methods.
Element ARSD（%） LOD（μg/mL） SHA-SD-
LIBSSHA-
LIBSLIBS SHA-SD-
LIBSSHA-
LIBSLIBS La 3.83 4.22 9.82 0.007 0.013 0.079 Er 4.47 5.23 10.33 0.045 0.065 0.697 Ce 4.29 4.47 11.38 0.011 0.015 0.398 Nd 4.31 4.37 9.74 0.019 0.029 0.608 Gd 4.87 4.93 10.74 0.041 0.053 0.755 Pr 4.18 4.32 9.71 0.008 0.013 0.079
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