Analysis of Trace Metal Elements in Water Based on Discharge-Assisted Laser-Induced Breakdown Spectroscopy
Xu Boping1,2, Liu Yinghua1,2, Liu Zaihao1,2, Yin Peiqi1,2, Tang Jie1,2
1. State Key Laboratory of Transient Optics and Photonics Xi'an Institute of Optics and Precision Mechanics of CAS Xi'an 710119 China; 2. University of Chinese Academy of Sciences Beijing 100049 China
Abstract：Heavy metal ion-induced water pollution has become a severe environment in the world. Laser-induced breakdown spectroscopy (LIBS) is a novel analytical technique based on the atomic emission spectroscopy, which can be used for the target in any state. Thus, LIBS is widely applied in various applications, including environmental pollution monitoring, food safety, and chemical engineering production. However, for liquid sample detection, the rapid quenching of the plasma, the contamination of the optical system by the unstable liquid level, and the limited laser energy absorption of the plasma have limited the further development of LIBS technology. Here, a discharge-assisted LIBS technique (D-LIBS) for the detection of trace elements in solutions is proposed and compared with the conventional LIBS (C-LIBS). Rapid sampling of mixed BaCl2 and NaCl2 solutions is performed using medium-speed filter paper. A Nd:YAG laser is implemented to generate plasmas containing the target elements on the filter paper. A discharge assistance consists mainly of a high voltage DC power supply, a capacitor, and a pair of rod electrodes. The capacitor is first charged by the high voltage DC power supply. The electrodes are respectively connected to the positive and negative terminals of the capacitor, and placed horizontally on the surface of the filter paper. Once the sample surface is ablated by the focused laser beam, the pre-existing plasma between the electrodes acts as the seed charged particles in the discharge gap, which rapidly ignites a strong discharge there. Compared to the time-integrated spectra in C-LIBS and D-LIBS, the LIBS signal has been greatly increased by using the discharge assistance. Emission lines of BaⅡ455.40 nm and NaⅠ588.99 nm are respectively enhanced to 30-fold and 6-fold. The spectral intensities in C-LIBS and D-LIBS are positively correlated with laser energy. However, the spectral enhancement factors show higher values at small laser energy conditions, and the BaⅡ spectral enhancement factor decreases from 30 (20 mJ) to 2 (50 mJ) with increasing laser energy. Compared with the spectral signal-to-noise ratio (SNR) in C-LIBS, D-LIBS results in a SNR enhancement of more than 1 order of magnitude. When the laser energy is 20 mJ, the SNR enhancement factor of BaⅡ spectral line and Na I spectral line is 56 and 16, respectively. In addition, the quantitative analysis performance of C-LIBS and D-LIBS for trace metal elements in solution under different laser energy conditions are comparatively studied. The limit of detection (LoD) of Ba is decreased along with the laser energy in C-LIBS, reaching 0.823 mg/L at 50 mJ. Moreover, under the optimal condition the LoD is reduced from 12.5 mg/L in C-LIBS to 0.26 mg/L in D-LIBS, and the detection sensitivity of LIBS technique is increased by 47-fold due to the discharge assistance. The following conclusions can be drawn from the experimental results: (1) The spectral intensity, SNR can be enhanced by over 1 order of magnitude. The increases in the intensity and SNR of the plasma spectra are due to the additional electrical energy injection resulting in the reheating and excitation of the plasma. (2) The spectral intensity and SNR are positively correlated with laser energy. The enhancement factor reaches the maximum in the smallest laser energy condition. This is due to the fact that the lower the laser energy, the smaller the mass of sample ablated, and therefore the more significant the enhancement effect is when the plasma is excited by the additional discharge. (3) The quantitative analysis of LIBS can be efficiently enhanced over 1 order of magnitude by the discharge assistance. And the LoD is reduced to 0.26 mg/L which is 1/48 of the original level.
许博坪, 刘颖华, 刘在浩, 尹培琪, 汤洁. 基于放电辅助激光诱导击穿光谱技术的水中痕量金属元素检测分析[J]. 电工技术学报, 2023, 38(17): 4757-4766.
Xu Boping, Liu Yinghua, Liu Zaihao, Yin Peiqi, Tang Jie. Analysis of Trace Metal Elements in Water Based on Discharge-Assisted Laser-Induced Breakdown Spectroscopy. Transactions of China Electrotechnical Society, 2023, 38(17): 4757-4766.
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2023, Vol. 38 
