High-Resolution Mass Spectrometry Study of the Bio-Oil Samples Produced by Thermal Liquefaction of Microalgae in Different Solvents
We have performed a comparative analysis of the bio-oil produced by thermal liquefaction of microalgae in different solvents using high-resolution Orbitrap mass spectrometry and GC-MS approach. Water, methanol, ethanol, butanol, isopropanol, acetonitrile, toluene, and hexane were used as solvents in which the liquefaction was performed. It was observed that all resulting oils demonstrate a considerable degree of similarity. For all samples, compounds containing 1 and 2 nitrogen atoms dominated in the positive ESI spectra, while a relative contribution of other compounds was small. In negative ESI mode, compounds having 2 to 7 oxygens were observed. Statistical analysis revealed that products can be combined in two groups depending on the solvent used for the liquefaction. To the first group, we can attribute the products obtained by using protic (alcohols) and to the second by using aprotic (acetonitrile, toluene) solvents. Nevertheless, based on our results, we concluded that solvent possesses a minor impact on molecular composition of bio-oil. We suggested that the driving force of the liquefaction reaction is the thermal dehydration of the carbohydrate in algae, resulting in water formation, which could be the trigger of the producing of bio-oil. To prove this hypothesis, we performed the reaction with the dry algae in the absence of the solvent and observed the formation of bio-oil.
KeywordsBio-oil Mass spectrometry Petroleum Dissolved organic matter FT ICR ESI
The investigation of the sample using ultrahigh resolution mass spectrometry was supported by Russian Science Foundation (grant no. 18-79-10127). The development of the liquefaction reactor was supported by Russian Science Foundation (grant no. 17-19-01617).
The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.
Compliance with Ethical Standards
The authors declare that they have no competing interests.
- 11.Vlaskin, M.S., Grigorenko, A.V., Kostyukevich, Y.I., Nikolaev, E.N., Vladimirov, G.N., Chernova, N.I., Kiseleva, S.V., Popel, O.S., Zhuk, A.Z.: Influence of solvent on the yield and chemical composition of liquid products of hydrothermal liquefaction of Arthrospira platensis as revealed by Fourier transform ion cyclotron resonance mass spectrometry. Eur. J. Mass Spectrom (Chichester). 24, 363–374. 469066718771209 (2018)CrossRefGoogle Scholar
- 12.Wang, Y., Nan, G., Wang, W., Zhang, J., Han, W.: Preparation and application of a new catalyst to produce bio-oil from microalgae liquefaction. Int. J. Agric. Biol. Eng. 10, 169–175 (2017)Google Scholar
- 21.Perminova, I.V., Dubinenkov, I.V., Kononikhin, A.S., Konstantinov, A.I., Zherebker, A.Y., Andzhushev, M.A., Lebedev, V.A., Bulygina, E., Holmes, R.M., Kostyukevich, Y.I., Popov, I.A., Nikolaev, E.N.: Molecular mapping of sorbent selectivities with respect to isolation of Arctic dissolved organic matter as measured by Fourier transform mass spectrometry. Environmental Science & Technology. 48, 7461–7468 (2014)CrossRefGoogle Scholar
- 24.Perminova, I.V., Dubinenkov, I.V., Kononikhin, A.S., Konstantinov, A.I., Zherebker, A.Y., Andzhushev, M.A., Lebedev, V.A., Bulygina, E., Holmes, R.M., Kostyukevich, Y.I.: Molecular mapping of sorbent selectivities with respect to isolation of arctic dissolved organic matter as measured by Fourier transform mass spectrometry. Environ. Sci. Technol. 48, 7461–7468 (2014)CrossRefGoogle Scholar
- 26.Sudasinghe, N., Dungan, B., Lammers, P., Albrecht, K., Elliott, D., Hallen, R., Schaub, T.: High resolution FT-ICR mass spectral analysis of bio-oil and residual water soluble organics produced by hydrothermal liquefaction of the marine microalga Nannochloropsis salina. Fuel. 119, 47–56 (2014)CrossRefGoogle Scholar
- 33.Zherebker, A.Y., Airapetyan, D., Konstantinov, A.I., Kostyukevich, Y.I., Kononikhin, A.S., Popov, I.A., Zaitsev, K.V., Nikolaev, E.N., Perminova, I.V.: Synthesis of model humic substances: a mechanistic study using controllable H/D exchange and Fourier transform ion cyclotron resonance mass spectrometry. Analyst. 140, 4708–4719 (2015)CrossRefGoogle Scholar
- 37.Popov, I.A., Nagornov, K., Vladimirov, G.N., Kostyukevich, Y.I., Nikolaev, E.N.: Twelve million resolving power on 4.7 T Fourier transform ion cyclotron resonance instrument with dynamically harmonized cell-observation of fine structure in peptide mass spectra. J. Am. Soc. Mass Spectrom. 25, 790–799 (2014)CrossRefGoogle Scholar
- 38.Kostyukevich, Y., Kononikhin, A., Popov, I., Starodubtzeva, N., Pekov, S., Kukaev, E., Indeykina, M., Nikolaev, E.: Analytical potential of the in-electrospray ionization source hydrogen/deuterium exchange for the investigation of oligonucleotides. Eur. J. Mass Spectrom. 21, 59–63 (2015)CrossRefGoogle Scholar
- 40.Kukaev, E., Kostyukevich, Y., Kononikhin, A., Indeykina, M., Popov, I., Nikolaev, E.: Supermetallization of peptides and proteins studied by high resolution mass spectrometry. Protein Sci. 25, 14–14 (2016)Google Scholar
- 41.Zherebker, A.Y., Kostyukevich, Y.I., Kononikhin, A.S., Nikolaev, E.N., Perminova, I.V.: Molecular compositions of humic acids extracted from leonardite and lignite as determined by Fourier transform ion cyclotron resonance mass spectrometry. Mendeleev Commun. 26, 446–448 (2016)CrossRefGoogle Scholar
- 46.Kostyukevich, Y., Vlaskin, M., Vladimirov, G., Zherebker, A., Kononikhin, A., Popov, I., Nikolaev, E.: The investigation of the bio-oil produced by hydrothermal liquefaction of Spirulina platensis using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry. Eur J. Mass Spectrom. 23, 83–88 (2017)CrossRefGoogle Scholar
- 51.Kostyukevich, Y., Zherebker, A., Kononikhin, A., Popov, I., Perminova, I., Nikolaev, E.: The investigation of the birch tar using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry and hydrogen/deuterium exchange approach. Int. J. Mass Spectrom. 404, 29–34 (2016)CrossRefGoogle Scholar
- 54.Vardon, D.R., Sharma, B.K., Scott, J., Yu, G., Wang, Z.C., Schideman, L., Zhang, Y.H., Strathmann, T.J.: Chemical properties of biocrude oil from the hydrothermal liquefaction of Spirulina algae, swine manure, and digested anaerobic sludge. Bioresour. Technol. 102, 8295–8303 (2011)CrossRefGoogle Scholar