Determination and study of correlations of relative sensitivity factors in metal and metal oxide samples by glow discharge mass spectrometry

The determination of relative sensitivity factor (RSF) plays a crucial role in achieving accurate quantitative analysis in glow discharge mass spectrometry (GD-MS). In this study, the RSF of typical elements in 14 metal and metal oxide matrices were determined, and their correlation with discharge parameters, matrix effects, the first ionization energies and sample shapes were investigated. It was found that discharge gas flow exerted a minor influence on RSF values in a nickel (Ni) metal sample, whereas discharge current significantly affected RSF, with variations up to 57.00 % for cobalt (59Co). The results revealed that matrix effects were more pronounced in metal oxides, with the relative standard deviation (RSD) of RSF for typical elements ranging from 25.17 % to 101.04 %. RSF values for the same element across different metal oxides showed a correlation with lattice binding energy (U0). Particularly, RSF values for 12 elements including 23Na, 27Al, 28Si, 45Sc, 52Cr, 56Fe, 59Co, 88Sr, 130Te, 138Ba, 139La and 140Ce within 7 metal oxides showed a significant correlation with U0 of the metal oxides. In terms of sample shape, pin samples generally yielded higher RSF values than flat samples in both metals and oxides. RSF accuracy was confirmed with standard samples of zirconium (Zr 73 MR10002 and Zr IARM 705-18) and iron oxides (Fe2O3-1 and Fe2O3-2) with relative errors within 17.50 % except for 12C. Subsequently, these RSF values were effectively utilized for the quantitative analysis of samples collected from the China Space Station (CSS). This comprehensive analysis elucidates the multifaceted influences on RSF values, enhancing the precision of trace element quantification in GD-MS.