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Calibration-Free Libs for Determination of the Mn/Fe Ratio in Ferromanganese Nodules with a Portable Diode-Pumped Solid-State Laser

Journal of Applied Spectroscopy, ISSN: 1573-8647, Vol: 89, Issue: 4, Page: 631-637
2022
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The Mn/Fe ratio, which serves as a marker of the contents of rare-earth and platinum-group elements in ferromanganese nodules, was determined in samples taken during expeditions in the Kara Sea and the Laptev Sea and in a set of certified reference materials (OOPE 601-604). The analysis was carried out by calibration-free laser-induced breakdown spectroscopy based on the use of plasma parameters and analytical line intensities of manganese and iron (Mn I 542.04 nm and Fe I 539.71 nm). The plasma temperature was determined using a Boltzmann plot. The electron density was determined using Stark broadening of the Fe I line at 538.34 nm. The ability to determine the Mn/Fe ratio in the range from 0.2 to 4.2 in ferromanganese nodules of various geographic origins was demonstrated. A high linear determination coefficient (R = 0.938) and proportionality between the results of calibration-free laser-induced breakdown spectroscopy and inductively coupled plasma atomic emission spectrometry (1:0.99) were achieved.

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