Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols.

The direct analysis of complex organic solid samples, such as coal, still represents a challenge for mass spectrometric researchers. In this work, we present an approach to analyze various carbonaceous samples with different degrees of coalification (one peat and five coals) using laser desorption/ionization in negative ion mode (LDI(−)) and ultrahigh resolving Fourier transform ion cyclotron resonance mass spectrometry. This preparation and analysis method enables a characterization of reactive organic molecules in their native state, without a need for excessive sample preparation or processing. By combining ultrahigh resolving mass spectrometry with different chemometric analyses, an in-depth characterization of the analyzed peat and coal samples was possible, and a correlation between the mass spectra and the degree of coalification of each sample could be verified. As a proof of concept, various analytical standard molecules were analyzed at increasing laser powers to demonstrate that the detected coal-related molecules are actually contained in the samples and were not simply formed by fragmentation reactions during the LDI process. Overall, the direct analysis method presented is a time-saving alternative to analyze complex organic solid samples of all kinds by mass spectrometry.

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Lignin is a complex macromolecule that possesses a high potential for various material-based applications in the near future. In order to retrieve this potential, more detailed knowledge about the structural composition of lignin is required. One possible way to solve this problem is the application of ultrahigh resolving analysis methods such as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). In most studies from the last years, mainly dissolved lignin compounds, which only represent a fraction of the overall sample, were utilized for MS investigations. In this study, both soluble and insoluble lignin compounds of three different lignins (Kraft and Lignoboost lignins) were analyzed by electrospray ionization (ESI) and graphite-assisted laser desorption/ionization (GALDI) in combination with FT-ICR-MS. The different MS analyses demonstrated that ESI- and liquid GALDI-MS analyses can assist in the characterization of lignin molecules, which possess a high solubility in solvents of high polarity. In contrast, solid GALDI-MS provides insights about less polar molecules that have a low solubility in most solvents. Due to this higher molecular range of analyzable lignin compounds, the novel results will, hopefully, help to improve our understanding of the lignin structure and to utilize this interesting biopolymer in a more expedient and efficient way in the future.