CI(+)FT-ICR MS analysis of hydrocarbons using isooctane as ionizing reagent - A comparison with HTGC-FID, GC×GC-MS and NMR

Abstract

Hydrocarbons present in saturated fractions of crude oils can be assessed by atmospheric pressure chemical ionization (APCI) using small hydrocarbons as ionizing reagents in a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). In this work, five paraffin standards of different average molar mass distributions (Mw) were easily ionized by APCI(+)FT-ICR MS using isooctane as the reagent gas. Data of Mw, carbon number and double bond equivalent (DBE) distributions corresponding to linear and cyclic hydrocarbons (HCs) were compared to results obtained from analysis of high temperature gas chromatography with a flame ionization detector (HTGC-FID), comprehensive two-dimensional gas chromatography coupled to mass spectrometry (GC×GC-MS) and 1 H and 13C nuclear magnetic resonance (NMR) spectroscopy. APCI(+)FT-ICR MS data showed good agreement with those of analytical techniques. Furthermore, the ability of APCI(+) to assess n-paraffin, even in blends with polyaromatic hydrocarbon molecules such as coronene (Mw = 301 Da) at concentrations from 2.5 to 25 µg mL-1, was demonstrated. The typical MS paraffin profile (containing repeating mass units of 14 Da) was clearly confirmed, being totally suppressed when a concentration of 25 µg mL-1 of coronene was used. This phenomenon was also evidenced in one of two saturated fractions produced using saturates, aromatics and polar (SAP) compound fractionation methodology.