Evaluating the effect of ion source gas (N2, He, and synthetic air) on the ionization of hydrocarbon, condensed aromatic standards, and paraffin fractions by APCI(+)FT-ICR MS

• Published in: Fuel (Guildford) Vol. 225; pp. 632 - 645
• Main Authors: Souza, Lindamara M., Tose, Lilian V., Cardoso, Felipe Mauro R., Fleming, Felipe P., Pinto, Fernanda E., Kuster, Ricardo M., Filgueiras, Paulo R., Vaz, Boniek G., Romão, Wanderson
• Format: Journal Article
• Language: English
• Published: Kidlington Elsevier Ltd 01-08-2018; Elsevier BV
• Subjects: Anthracene; APCI; Aromatic compounds; Aromatic hydrocarbons; Cyclotron resonance; Dicarboximide; Effects; Electron transfer; Fourier transforms; FT-ICR mass spectrometry; Gases; Helium; Hydrides; Hydrocarbon; Hydrocarbons; Ion source gas; Ionization; Ions; Isooctane; Mass spectra; Mass spectrometry; Mass spectroscopy; Nitrogen; Noise; Organic chemistry; Oxidation; Paraffin; Paraffins; Reagents; Squalene; APCI; Hydrocarbon; Paraffin; Ion source gas; FT-ICR mass spectrometry
• ISSN: 0016-2361; 1873-7153
• DOI: 10.1016/j.fuel.2018.03.180

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This study aimed to use different types of ion source gases [synthetic air, nitrogen (N2), and helium (He)] to compare the ionization efficiency of linear, branched, and cyclic hydrocarbon (HC) standards (i.e., hexatriacontane, squalene, and 5-α-cholestane, respectively), condensed aromatics (CA) standards (i.e., coronene, benz[a]anthracene, and n,n′-bis(3-pentyl)perylene-3,4,9,10-bis(dicarboximide)), one n-paraffin standard, containing carbon numbers ranging from C5 to C120, and two saturated HC fractions. In all cases, a positive-ion mode atmospheric pressure chemical ionization coupled to a Fourier transform ion cyclotron resonance mass spectrometer was used. Isooctane reagent was used to facilitate the ionization of n-paraffins. Three ionization mechanisms were observed: electron transfer ([M]rad+), proton transfer ([M+H]+), and hydride abstraction ([M−H]+). For the ionization of HC standards, synthetic air and He gases presented better ionization efficiency and produced mass spectra with greater mass accuracy and signal-to-noise rate. Moreover, linear HCs were preferentially ionized through hydride abstraction (production of [M−H]+ ions), whereas the ionization of unsaturated and cyclic HCs mostly occurred through the production of [M+H]+ and [Mrad+] species. The unique exception is related to 5-α-cholestane, which is ionized as [M−H]+ in the presence of synthetic air. For the CA standards, N2 and synthetic air promoted the detection of CA standards mainly by electron transfer mechanism, [M]rad+ species. Conversely, He favored the proton transfer ionization ([M+H]+) with minimal fragmentation or oxidation of the analyte. In all cases, synthetic air provided mass spectra with excellent signal-to-noise ratio. This performance was attributed to the high reactive-ionizing power of O2 gas over the HC and CA molecules. For the n-paraffin samples, synthetic air and He provided better ionization performance through hydride abstraction ([M−H]+). N2 favored the production and ionization of heteroatomic compound classes (Ox and NOx).