Matrix effect based on laser-induced breakdown spectroscopy
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摘要: 为分析和改善激光诱导击穿光谱技术(LIBS)在定量分析土壤和大米中镉(Cd)元素含量时基体效应对分析结果的影响,以Cd Ⅱ 226.502 nm谱线为分析对象,对比研究了基体种类、KCl质量分数和激发方式等对Cd Ⅱ 226.502 nm谱线强度和定量分析结果的影响规律。研究结果表明:基体主成分的化学形态和电离能是产生基体效应的主要因素,KCl作为添加剂能明显改善大米中Cd Ⅱ 226.502 nm的谱线强度,光电双脉冲激发能显著增强基体中Cd Ⅱ 226.502 nm的谱线强度、稳定性并提高信噪比。与单激光脉冲激发方式相比,在光电双脉冲激发下,SiO2、土壤和大米三种基体中Cd Ⅱ 226.502 nm的检测下限分别从372、332和2874 mg·kg−1降低到42、72和37 mg·kg−1。Abstract: To analyze and improve the matrix effect on the quantitative analysis of cadmium (Cd) concentration in soil and rice using laser induced breakdown spectroscopy (LIBS), this article takes the Cd Ⅱ 226.502 nm spectral line as the analysis object, and compares the effects of matrix type, KCl mass concentration, and excitation method on the intensity and quantitative analysis results of Cd Ⅱ 226.502 nm spectral line. The results show that the chemical form of the main components of the matrix and the ionization energy are the main factors that produce the matrix effect. KCl as an additive can significantly improve the spectral line intensity of Cd Ⅱ 226.502 nm in rice. The photoelectric double pulse excitation can significantly enhance the spectral line intensity and stability of Cd Ⅱ 226.502 nm in the matrix, and improve the signal to noise ratio. Compared with the single laser pulse excitation method, the lower detection limit of Cd Ⅱ 226.502 nm in silicon dioxide, soil, and rice matrices decreased from 372, 332 and 2874 mg·kg−1 to 42, 72 and 37 mg·kg−1, respectively, under photoelectric dual pulse excitation. This study has important reference value for the development of LIBS technology and its application and promotion in the field of soil and food pollution detection.
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Key words:
- matrix effect /
- chemical bond /
- ionization energy /
- atomization /
- plasma parameter
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表 1 D和E组标准样品中镉元素和氯化钾的质量分数
Table 1. Mass fractions of cadmium and potassium chloride in standard samples of groups D and E
sample mass fraction/% sample mass fraction/% Cd KCl Cd KCl D1 1 0 E1 0.2 0 D2 1 3 E2 0.2 3 D3 1 6 E3 0.2 6 D4 1 9 E4 0.2 9 D5 1 12 E5 0.2 12 表 2 F、G和H三组标准样品中镉元素的质量分数
Table 2. Mass fractions of cadmium in three groups (F, G, and H) of standard samples
sample mass fraction/% sample mass fraction/% sample mass fraction/% F1 0.004 G1 0.004 H1 0.004 F2 0.010 G2 0.010 H2 0.010 F3 0.020 G3 0.020 H3 0.020 F4 0.040 G4 0.040 H4 0.040 F5 0.100 G5 0.100 H5 0.100 F6 0.200 G6 0.200 H6 0.200 F7 0.400 G7 0.400 H7 0.400 − − − − H8 1.000 − − − − H9 2.000 表 3 三种基体在两种激发方式下的定量分析结果
Table 3. Quantitative analysis results of three matrices under two excitation methods
LOD / (mg·kg−1) R2 /% RSD / % 355 nm OEDB-LIBS 355 nm OEDB-LIBS 355 nm OEDB-LIBS Group F sample (silica matrix) 372 42 93.5 97.6 13.604 7.232 Group G sample (soil matrix) 332 72 84.0 94.5 14.283 7.691 Group H sample (rice matrix) 2874 37 95.3 95.1 13.544 6.968 -
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