Advanced mono‐ and multi‐dimensional gas chromatography–mass spectrometry techniques for oxygen‐containing compound characterization in biomass and biofuel samples

Abstract

A wide variety of biomass, from triglycerides to lignocellulosic‐based feedstock, are among promising candidates to possibly fulfill requirements as a substitute for crude oils as primary sources of chemical energy feedstock. During the feedstock processing carried out to increase the H:C ratio of the products, heteroatom‐containing compounds can promote corrosion, thus limiting and/or deactivating catalytic processes needed to transform the biomass into fuel. The use of advanced gas chromatography techniques, in particular multi‐dimensional gas chromatography, both heart‐cutting and comprehensive coupled to mass spectrometry, has been widely exploited in the field of petroleomics over the past 30 years and has also been successfully applied to the characterization of volatile and semi‐volatile compounds during the processing of biomass feedstock. This review intends to describe advanced gas chromatography–mass spectrometry‐based techniques, mainly focusing in the period 2011–early 2020. Particular emphasis has been devoted to the multi‐dimensional gas chromatography–mass spectrometry techniques, for the isolation and characterization of the oxygen‐containing compounds in biomass feedstock. Within this context, the most recent advances to sample preparation, derivatization, as well as gas chromatography instrumentation, mass spectrometry ionization, identification, and data handling in the biomass industry, are described.

Review on Evolved Gas Analysis Mass Spectrometry with Soft Photoionization for the Chemical Description of Petroleum, Petroleum-Derived Materials, and Alternative Feedstocks

“…82 Nonetheless, GCMS platforms are dominated by harsh electron ionization conducted at 70 eV (EI), and to date, only a limited number of soft ionization approaches exist, with chemical ionization, soft electron ionization, and photoionization as the most important schemes. For the general concept of gas chromatography, the reader is directed to excellent recent reviews, discussing applications in biomass and biofuel analysis, 18,83 and Tranchida et al reviewed comprehensive gas chromatography with special emphasis toward ionization techniques. 84 Here, the importance of soft vacuum ionization concepts, such as soft EI, and atmospheric pressure solutions, such as GC−APCI, are presented.…”

“…Here, the authors discuss in detail the technical development of ultrahigh-resolution mass spectrometric instrumentation but also focus toward experimental protocols and data analysis procedures. Furthermore, in the context of bio-oil analysis, a review on the comprehensive gas chromatographic investigation of those materials was recently presented . Other reviews covering the mass spectrometric analysis of fossil petroleum, , solid fuels, and alternative sources feature ultrahigh-resolution mass spectrometry, ion mobility coupling, or spray-based ionization concepts …”

“…Furthermore, in the context of bio-oil analysis, a review on the comprehensive gas chromatographic investigation of those materials was recently presented. 18 Other reviews covering the mass spectrometric analysis of fossil petroleum, 19,20 solid fuels, 21 and alternative sources feature ultrahigh-resolution mass spectrometry, ion mobility coupling, or spray-based ionization concepts. 22 Evolved gas analysis mass spectrometry with soft ionization is increasingly used for the chemical description of petroleum, petroleum-derived materials, solid fuels, bio oils, and pyrolysis oils.…”

Review on Aging of Bio-Oil from Biomass Pyrolysis and Strategy to Slowing Aging

“…Mass spectrometry (MS) is usually coupled with GC and LC to decipher compositional complexities of bio-oil to a large extent . GC-based detection facilitates the characterization of volatile and semivolatile bio-oil compounds . Two-dimensional GC uses the combination of two chromatographic columns connected via a modulator, which can provide a much more detailed bio-oil characterization than GC .…”

“…79 GC-based detection facilitates the characterization of volatile and semivolatile biooil compounds. 80 Two-dimensional GC uses the combination of two chromatographic columns connected via a modulator, which can provide a much more detailed bio-oil characterization than GC. 81 LC-based detection can be used to analyze the entire bio-oil, including volatile, less-volatile, and highmolecular-weight compounds.…”