Development of a Tube Plasma Ion Source for Gas Chromatography–Mass Spectrometry Analysis and Comparison with Other Atmospheric Pressure Ionization Techniques

A tube plasma ionization (TPI) open-air source for gas chromatography–mass spectrometry (GC–MS) was developed. This source is based on an inverse low temperature plasma configuration where the pin inner electrode is applying the high voltage and the grounded electrode is the housing itself. The ionization possibilities were tested by using an EPA mix of priority contaminants, showing that 68% of the analytes could undergo both proton-transfer and charge-exchange reactions. The potential of using different discharge gases (He and Ar) to ionize the analytes and auxiliary gases (He, N₂, O_2, and synthetic air) to transport the ions toward the MS was carefully investigated. Additionally, the addition of water was also tested to show the different ionization trends in the TPI source. Finally, the ionization by TPI under both dry and wet conditions was compared with other gas-phase atmospheric pressure ionization sources showing TPI could ionize a wider range of compounds (97%) than atmospheric pressure chemical ionization (APCI, 95%) and atmospheric pressure photoionization (APPI, 87%). Besides, the detection capability of TPI was better than APCI and APPI, achieving instrumental limits of detection down to 3 fg on column, which demonstrates the great potential of this ionization source for GC–MS determinations.