Mass Spectrometry‐based Techniques for Direct Quantification of High Ionization Energy Elements in Solid Materials—challenges and Perspectives

Abstract

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.

Excitation and ionization processes of chlorine in molybdenum dichloride dioxideflakesusing the glow discharge mass spectrometry technique

“…to the amount of the constituent element in the sample) have probably higher ionization efficiency as compared to the other elements in argon plasma. The general impression about chlorine is that due to the higher ionization energy and higher electronegativity, it has lower ionization rates in argon plasma, 30 however, contrary to expectations a different behaviour is noticed here. It should be noted that the most probable ionization process is only electron impact ionization of the chlorine ground state.…”

“…Therefore, in general, chlorine has lower sensitivity as compared to most metallic constituent elements present in the matrix. 30,31 The most intense atomic emission lines of chlorine either require vacuum-UV (for 132.72 nm) or NIR (for 837.59 nm) sensitive detection systems. Additionally, the complication in chlorine quantication further arises when it is present in the matrix as a constituent element in ultratrace amounts.…”

New Possibilities for the Determination of Volatile Organic Compounds by Their Molecular Ions in Air Using µs-Pulsed GD TOFMS

“…Under such repelling pulse delay, the ions formed by the high-energy electron packet are detected. 11,17,18 The flow of the high-energy electron packet is formed at the front of the discharge pulse and is capable to ionise the components with the highest ionisation energies. 9,11 The obtained mass spectrum (Fig.…”

Volatile Organic Compound Fragmentation in the Afterglow of Pulsed Glow Discharge in Ambient Air

“…Recently, glow discharge (GD) sources, formerly considered mainly as a source suitable for inorganic and isotopic analysis [ 17 ], have gained an increased level of attention in relation to the analysis of VOCs and volatile inorganic molecules mixtures [ 18 ]. Nunome et al [ 4 , 19 ] reported the determination of VOCs in the air using a Soft Penning ionization (SPI) GD source.…”