Volatile organic compound analysis by pulsed glow discharge time of flight mass spectrometry as a structural elucidation tool

Pulsed glow discharge (PGD) coupled to time of flight mass spectrometry (TOFMS) has been investigated for volatile organic compound (VOC) identification and determination. Optimization of PGD operational conditions (chamber design, applied power, pressure and duty cycle) was performed using acetone and benzene as model compounds. During the different optimizations, molecular, fragment and elemental information were obtained when characteristic GD pulse regions were measured. An exploratory study for several VOCs (lineal hydrocarbons, oxygen‐containing compounds and aromatic compounds) revealed the capability of the PGD to provide crucial information to elucidate structures (fragments), molecular ions or even proton affinity nature of the molecules; this last information is a consequence of the enriched proton environment generated along the afterglow region for the ionization chamber used. Analytical characteristics were evaluated with solid phase microextraction–gas chromatography coupled to PGD‐TOFMS for special aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylene: BTEX) in water, showing a good performance in terms of reproducibility and sensitivity. Copyright © 2017 John Wiley & Sons, Ltd.