Contribution of atmospheric pressure chemical ionization mass spectrometry for the characterization of bio-oils from lignocellulosic biomass: Comparison with electrospray ionization and atmospheric pressure photoionization

Bio-oils obtained from lignocellulosic biomass pyrolysis present a very promising alternative to replace petroleum-based fuels. At the molecular level, these materials are highly complex organic mixtures comprising thousands of species covering a large range of mass and polarity. Compared to petroleum, they present a high amount of oxygen containing compounds, limiting their direct use in the classical refining system. To understand and improve both the conversion and upgrading processes, an advanced molecular description of the raw and upgraded bio-oils is required. The most powerful technique for the molecular characterization of such sample is Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS), thanks to its very high mass accuracy and resolving power. It allows assigning unambiguously a unique molecular formula to each m/z signal. Besides, the use of different ionization sources ensures an extensive molecular description and enables to assess the efficiency of different catalytic chemical treatments. In this study, we report the characterization of a pine pyrolysis bio-oil by the three main atmospheric pressure ionization sources: electrospray (ESI), atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) in positive mode coupled to FTICR analyzer. In addition, different solvents and dopants were used to ensure a comprehensive description of the molecular content. Regardless of the atmospheric pressure ionization sources used, C0–100H0–300O0–15 molecular formulas are mainly obtained with lignocellulosic biomass-based bio-oils. Nevertheless, depending on the ionization source, the ions relative intensity are significantly different in respect with their double bound equivalent (DBE), oxygen to carbon ratio (O/C) and hydrogen to carbon ratio (H/C). For example, the APPI source has shown the efficient ionization of aromatic (high DBE and low H/C) less polar (low O/C) molecules compared to the ESI source which efficiency ionized more polar species with high oxygen atom content (high O/C). APCI source has proven to be particularly useful for bio-oil characterization as it demonstrates the presence of an aliphatic distribution in addition to the other bio-oil components also ionized by APPI and ESI.