Abstract
In this paper, we presented a detailed study on the effect of electron beam diameter, spectral overlapping, and element assay sequence on quantitative uncertainties of electron probe microanalysis. With a fixed electron beam diameter of 1 μm for external standard materials, the sample signal intensities were found to decline with the increasing electron beam diameter from 1 to 300 μm, resulting in a sample concentration bias higher than 2% and even up to 20%. Only when electron beam diameter difference between external standard materials and analyzed samples was less than 20 μm, the concentration bias was negligible. The spectral overlapping interference investigation revealed that in the case of shoulder-peak overlapping it was possible to remove the concentration bias by appropriately choosing L value and background signal picking-up position. However, quantification calibration was mandatory when there existed on-peak spectral overlapping interference. For sphalerite samples, this effect was prominent, and the artificially produced Na2O concentration can be 6.23% (±0.30%, 2σ, n = 12) due to on-peak spectral interference of Zn on Na. Furthermore, because of the on-peak spectral interference of S on Mo, the quantification accuracy of Mo was found to be dependent on the mass fraction of S in the studied samples. We also observed that element assay sequence highly affected the quantification accuracy of geological samples containing alkali. In element composition analysis of albite samples, when using matrix-matched calibration standard, the average Na2O concentration decreased substantially from 11.55 to 5.61% when Na was measured the first and last, respectively.
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ACKNOWLEDGMENTS
We highly appreciate the constructive comments from anonymous reviewers and the editor.
Funding
The authors also gratefully acknowledge the financial support from the Natural Science Foundation, China (no. 4210030145), the National Key Research and Development Project, China (no. 2019YFC0605202 and no. 2021YFC2901902), and the Natural Science Basic Research Program of Shaanxi Province, China (no. 2020JQ-974).
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Liu, M., Tan, X. Uncertainty of the Results of Electron Probe Microanalysis using a Spectrometer with Wavelength Dispersion in the Study of Geological Samples. J Anal Chem 77, 1333–1339 (2022). https://doi.org/10.1134/S1061934822100094
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DOI: https://doi.org/10.1134/S1061934822100094