MASS SPECTROMETRY-BASED TECHNIQUES FOR DIRECT QUANTIFICATION OF HIGH IONIZATION ENERGY ELEMENTS IN SOLID MATERIALS-CHALLENGES AND PERSPECTIVES.

The determination of nonmetals, first of all, the most electronegative ones-nitrogen, oxygen, fluorine, chlorine, and bromine, poses the highest challenge for element analysis. These elements are characterized by high reactivity, volatility, high ionization energy, and the absence of intensive spectral lines in the optical spectral range. Conventional techniques of their quantification include considerable "wet chemistry" stages so the application of these techniques for the solid sample is highly laborious and prone to uncontrollable uncertainties. Additionally, current development in material science and other areas requires the quantification of the elements at lower levels with good sensitivity. Owing to their robustness and flexibility, mass spectrometry techniques provide vast possibilities for the quantification, spatial and isotopic analysis, including the solutions for direct analysis of solids. The current review focuses on the application of major mass spectrometric techniques for the quantification of N, O, F, Cl, and Br in solid samples. The following techniques are mainly considered: thermal ionization mass spectrometry (TIMS), isotope-ratio MS (IRMS), secondary ion MS (SIMS), inductively coupled plasma MS (ICP-MS), and glow discharge MS (GDMS); as the most accessible and widely applied for the purpose. General ionization issues, advantages, limitations, and novel methodological solutions are discussed. © 2020 John Wiley & Sons Ltd.