Temperature-Dependent Lipid Conversion and Nonlipid Composition of Microalgal Hydrothermal Liquefaction Oils Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry
We illustrate a detailed compositional characterization of hydrothermal liquefaction (HTL) oils derived from two biochemically distinct microalgae, Nannochloropsis gaditana and Chlorella sp. (DOE 1412), for a range of reaction temperature as observed by high-resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The unique capability to unequivocally derive molecular formulae directly from FT-ICR MS-measured mass-to-charge ratio (for several thousand compounds in each oil) shows that lipids are completely reacted/converted for any reaction temperature above 200 °C and reveals the formation of nonlipid reaction products with increasing temperature. Specifically, lipid-rich oil is obtained at low reaction temperature (<225 °C) for both microalgal strains. For positive ion mode, the major lipid components in Chlorella sp. and N. gaditana HTL oils are betaine lipids and acylglycerols, respectively. Acidic species in the HTL oils (observed by negative ion mode) are dominated by free fatty acids (FFA) regardless of reaction temperature. HTL oils obtained at higher temperatures (≥225 °C) are composed of a variety of basic nitrogen- and oxygen-containing compounds that originate from protein and carbohydrate degradation at elevated temperature. Similar structural features are observed for the abundant nitrogen heterocyclics between the two strains with slightly lower carbon number for Chlorella sp., overall.
KeywordsNannochloropsis Chlorella Hydrothermal liquefaction Lipids FT-ICR MS Mass spectrometry
The authors thank Barry Dungan for providing FAME quantitation and Omar Holguin for helpful discussion. This work was supported by the US Department of Energy under contract DE-EE0003046 awarded to the National Alliance for Advanced Biofuels and Bioproducts, the National Science Foundation (IIA-1301346), the NMSU Agricultural Experiment Station and the Center for Animal Health and Food Safety at New Mexico State University.
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