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Temperature-Dependent Lipid Conversion and Nonlipid Composition of Microalgal Hydrothermal Liquefaction Oils Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

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Abstract

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.

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Acknowledgments

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.

Author information

Author notes

  1. Harvind Reddy

    Present address: Tucker Energy Services, Inc., 7299 US-270, McAlester, OK, 74501, USA

  2. Nicholas Csakan & Peter Lammers

    Present address: Arizona Center for Algal Technology and Innovation, Arizona State University, Tempe, AZ, 85281, USA

Authors and Affiliations

  1. Chemical Analysis and Instrumentation Laboratory, College of Agricultural, Consumer and Environmental Sciences, New Mexico State University, 945 College Ave., Las Cruces, NM, 88003, USA

    Nilusha Sudasinghe & Tanner Schaub

  2. Department of Chemical and Materials Engineering, New Mexico State University, P.O. Box 30001, MSC 3805, Las Cruces, NM, 88003, USA

    Harvind Reddy & Shuguang Deng

  3. Energy Research Laboratory, New Mexico State University, P.O. Box 30001, MSC 3RES, Las Cruces, NM, 88003, USA

    Nicholas Csakan & Peter Lammers

Authors
  1. Nilusha Sudasinghe
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  2. Harvind Reddy
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  3. Nicholas Csakan
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  4. Shuguang Deng
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  5. Peter Lammers
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  6. Tanner Schaub
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Corresponding author

Correspondence to Tanner Schaub.

Electronic Supplementary Material

Below is the link to the electronic supplementary material.

Online Resource 1

Positive-ion ESI MS2 spectrum of 16:0 monoacylglyceryl-N,N,N-trimethylhomoserine (MGTS) (top) and MS3 spectrum of 456 Da ion from Chlorella sp. HTL oil produced at 180 °C (PDF 36 kb)

Online Resource 2

Positive-ion ESI MS2 spectrum of 16:0/20:5 diacylglyceryl-N,N,N-trimethylhomoserine (DGTS) (top) and 16:0/16:1 DGTS (bottom) from Chlorella sp. HTL oil produced at 180 °C (PDF 48 kb)

Online Resource 3

Positive-ion ESI MS2 spectrum of 16:0/16:1 diacylglycerol (DAG) (top) and 16:0/16:0/16:1 TAG (bottom) from N. gaditana HTL oil produced at 180 °C (PDF 126 kb)

Online Resource 4

Acid- and base-catalyzed FAME profiles for N. gaditana (top) and Chlorella sp. (bottom) biomass (PDF 42 kb)

Online Resource 5

Negative-ion ESI FT-ICR MS abundance-contoured plots of DBE versus carbon number for oxidized fatty acids observed for Chlorella sp. (left) and N. gaditana (right) HTL oils produced at 300 °C (PDF 43 kb)

Online Resource 6

Negative-ion ESI MS2 spectrum of the predominant O5 sulfate lipid (C32H65O5S1) (top) and O4 sulfate lipid (C32H63O4S1) (bottom) from N. gaditana HTL oil produced at 180 °C (PDF 38 kb)

Online Resource 7

Negative-ion ESI MS2 spectrum of 16:0 sulfoquinovosyl monoacylglycerol (SQMG) from Chlorella sp. HTL oil produced at 180 °C (PDF 29 kb)

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Sudasinghe, N., Reddy, H., Csakan, N. et al. Temperature-Dependent Lipid Conversion and Nonlipid Composition of Microalgal Hydrothermal Liquefaction Oils Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Bioenerg. Res. 8, 1962–1972 (2015). https://doi.org/10.1007/s12155-015-9635-9

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  • DOI: https://doi.org/10.1007/s12155-015-9635-9

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