Abstract：Total reflection X-ray fluorescence spectroscopy (TXRF) technology usually uses internal standard method for quantitative analysis. It is not always easy to select an internal standard element in practical applications. Additionally, the sample preparation process can be cumbersome, which is not conducive to field analysis. Therefore, this article proposes a rapid TXRF quantitative analysis method that eliminates the need for internal standard addition by utilizing Ar, which is constantly present in the air, as the internal standard element for quantitative calculation.A rapid TXRF quantitative analysis method for Cr, Mn, Ni, Cu, Zn, Sr, and other elements in groundwater samples without internal standard addition was established. Blank sample tests were conducted on 24 quartz reflectors, revealing minimal variation in the total and net intensities of Ar, with precision values of 1.05% and 1.09%, respectively. This provides theoretical and operational feasibility for using Ar as an internal standard element. Under the specified measurement conditions, the limits of detection (LODs) of Cr, Mn, Ni, Cu, Zn, and Sr were all less than 2.00 μg·L-1, and the precision of each element was better than 10%. TXRF measurements of five different concentrations of M22809 standard solutions showed that the TXRF values obtained using Ar as the internal standard and those using Ga as the internal standard were consistent with the certified values, demonstrating the feasibility of using Ar as an internal standard element for TXRF quantitative analysis. Further validation was performed by analyzing three groundwater samples, where the TXRF results using Ar or Ga as the internal standard were in good agreement with ICP-MS measurements, confirming the reliability of using Ar as an internal standard element. On-site TXRF analysis of four groundwater samples in Laizhou, Yantai, TXRF results consistent with ICP-MS measurements, demonstrating the effectiveness of the method for field applications. When using Ar as an internal standard element for TXRF quantitative analysis, to improve the accuracy, it is necessary to first measure the standard solution in parallel three times to determine the Ar concentration value. However, since Ar and Cl are adjacent elements,high Cl content in samples may cause spectral overlap, which can affect the quantitative analysis results. Therefore, when using Ar as an internal standard element for TXRF quantitative analysis, it is generally suitable for samples with relatively simple matrices, such as groundwater, mineral water, and other clean water samples. This method is rapid and reliable, providing technical support for rapid on-site analysis of water samples.
Key words：Total reflection X-ray fluorescence spectrometry;Without internal standard addition;Ar;Rapid;Quantitative analysis;Groundwater
刘 晓，储彬彬，樊兴涛，詹秀春. 无内标添加全反射X射线荧光光谱快速定量分析方法研究[J]. 光谱学与光谱分析, 2025, 45(11): 3169-3173.
LIU Xiao, CHU Bin-bin, FAN Xing-tao, ZHAN Xiu-chun. Research on Rapid Quantitative Analysis Method of Total Reflection
X-Ray Fluorescence Spectroscopy Without Internal Standard Addition. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(11): 3169-3173.
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