Analytical and Bioanalytical Chemistry

, Volume 409, Issue 14, pp 3527–3539 | Cite as

A green analytical chemistry approach for lipid extraction: computation methods in the selection of green solvents as alternative to hexane

  • Mari Merce Cascant
  • Cassandra Breil
  • Salvador Garrigues
  • Miguel de la GuardiaEmail author
  • Anne Silvie Fabiano-Tixier
  • Farid ChematEmail author
Research Paper


There is a great interest in finding alternatives and green solvents in extraction processes to replace petroleum based solvents. In order to investigate these possibilities, computational methods, as Hansen solubility parameters (HSP) and conductor-like screening model for real solvent (COSMO-RS), were used in this work to predict the solvation power of a series of solvents in salmon fish lipids. Additionally, experimental studies were used to evaluate the performance in lipids extraction using 2-methyltetrahydrofurane, cyclopentyl methyl ether, dimethyl carbonate, isopropanol, ethanol, ethyl acetate, p-cymene and d-limonene compared with hexane. Lipid classes of extracts were obtained by using high performance thin-layer chromatography (HPTLC), whereas gas chromatography with a flame ionization detector (GC/FID) technique was employed to obtain fatty acid profiles. Some differences between theoretical and experimental results were observed, especially regarding the behavior of p-cymene and d-limonene, which separate from the predicted capability. Results obtained from HPTLC indicated that p-cymene and d-limonene extract triglycerides (TAGs) and diglycerides (DAGs) at levels of 73 and 19%, respectively, whereas the other studied extracts contain between 75 and 76% of TAGs and between 16 and 17% of DAGs. Fatty acid profiles, obtained by using GC-FID, indicated that saturated fatty acids (SFAs) between 19.5 and 19.9% of extracted oil, monounsaturated fatty acids (MUFAs) in the range between 43.5 and 44.9%, and PUFAs between 31.2 and 34.6% were extracted. p-Cymene and limonene extracts contained lower percentages than the other studied solvents of some PUFAs due probably to the fact that these unsaturated fatty acids are more susceptible to oxidative degradation than MUFAs. Ethyl acetate has been found to be the best alternative solvent to hexane for the extraction of salmon oil lipids.

Graphical Abstract


Green alternative solvent n-Hexane Cosmo-RS Hansen parameters Salmon fish Lipid extraction 



M.C. acknowledges the FPI grant (BES-2012-055404) and (EEBB-I-16-11854) provided by the Ministerio de Economia y Competividad of the Spanish government. The financial support of the Generalitat Valenciana (Project PROMETEO II 2014/077) is also acknowledged.

Compliance with Ethical Standards

Conflict of interest

The authors declare that they have no conflict of interest.

Samples from salmon already harvested were acquired in the supermarket. Thus, no ethical permits were needed (Directive 2010/63/EU).


  1. 1.
    Manirakiza P, Covaci A, Schepens P. Comparative study on total lipid determination using Soxhlet, Roese-Gottlieb, Bligh & Dyer, and Modified Bligh & Dyer extraction methods. J Food Compos Anal. 2001;14:93–100.CrossRefGoogle Scholar
  2. 2.
    Henriques J, Dick JR, Tocher DR, Bell JG. Nutritional quality of salmon products available from major retailers in the UK: content and composition of n-3 long-chain PUFA. Br J Nutr. 2014;112:964–75.CrossRefGoogle Scholar
  3. 3.
    Pando ME, Auborg SP. Concentrating n-3 fatty acids from crude and refined commercial salmon oil. Czech J Food Sci. 2014;32:169–76.Google Scholar
  4. 4.
    Vinagre J, Rodríguez A, Larraín MA, Aubourg SP. Chemical composition and quality loss during technological treatment in coho salmon (Oncorhynchus kisutch). Food Res Int. 2011;44:1–13.CrossRefGoogle Scholar
  5. 5.
    Lavie CJ, Milani RV, Mehra MR, Ventura HO. Omega-3 polyunsaturated fatty acids and cardiovascular diseases. J Am Coll Cardiol. 2009;54:585–94.CrossRefGoogle Scholar
  6. 6.
    Strobel C, Jahreis G, Kuhnt K. Survey of n-3 and n-6 polyunsaturated fatty acids in fish and fish products. Lipids Health Dis. 2012;11:144.CrossRefGoogle Scholar
  7. 7.
    Calder PC. Very long chain omega-3 (n-3) fatty acids and human health. Eur J Lipid Sci Technol. 2014;116:1280–300.CrossRefGoogle Scholar
  8. 8.
    Kaur G, Cameron-Smith D, Garg M, Sinclair AJ. Docosapentaenoic acid (22:5n-3): a review of its biological effect. Prog Lipid Res. 2011;50:28–34.CrossRefGoogle Scholar
  9. 9.
    Sahena F, Zaidul ISM, Jinap S, et al. PUFAs in fish: extraction, fractionation, importance in health. Compr Rev Food Sci Food Saf. 2009;8:59–74.CrossRefGoogle Scholar
  10. 10.
    Abdulkadir M, Abubakar GI, Mohammed. Production and characterization of oil from fishes. J Eng Appl Sci. 2010;5:1–5.Google Scholar
  11. 11.
    Regulation (EC) No. 1272/2008 of the European Parliament and of the Council of 16 December 2008 on classification, labeling, and packaging of substances and mixtures.Google Scholar
  12. 12.
    Public Health Statement, n-Hexane. Public Health Service Agency Toxic Substance Dis. Registration.Google Scholar
  13. 13.
    Chemat F, Abert Vian M (eds). Alternative solvents for natural products extraction, green chemistry and sustainable technology. Springer-Verlag, Berlin Heidelberg; 2014.Google Scholar
  14. 14.
    Virot M, Tomao V, Ginies C, Chemat F. Total lipid extraction of food using d-limonene as an alternative to n-hexane. Chromatographia. 2008;68:311–3.CrossRefGoogle Scholar
  15. 15.
    Bertouche S, Tomao V, Hellal A, Boutekedjiret C, Chemat F. First approach on edible oil determination in oilseeds products using alpha-pinene. J Essent Oil Res. 2013;25:439–43.CrossRefGoogle Scholar
  16. 16.
    Breil C, Meullemiestre A, Vian M, Chemat F. Bio-based solvents for green extraction of lipids from oleaginous yeast biomass for sustainable aviation biofuel. Molecules. 2016;21:1–14.CrossRefGoogle Scholar
  17. 17.
    Sicaire AG, Abert Vian M, Fine F, Carré P, Tostain S, Chemat F. Experimental approach versus COSMO-RS assisted solvent screening for predicting the solubility of rapeseed oil. OCL. 2015;22:D404.Google Scholar
  18. 18.
    Li Y, Fine F, Fabiano-Tixier AS, et al. Evaluation of alternative solvents for improvement of oil extraction from rapeseeds. Comptes Rendus Chim. 2014;17:242–51.CrossRefGoogle Scholar
  19. 19.
    Hansen CM. Hansen solubility parameters. A User’s Handbook. 2nd ed. Boca Raton: CRC press, Taylor & Francis Group; 2007.Google Scholar
  20. 20.
    Klamt A. The COSMO and COSMO-RS solvation models. Wiley Interdiscipl Rev Comput Mol Sci. 2011;1:699–709.CrossRefGoogle Scholar
  21. 21.
    Gupta AVJP. Sustainable bio­ethanol production from agro-residues: a review. Renew Sustain Energy Rev. 2015;41:550–67.CrossRefGoogle Scholar
  22. 22.
    Colley SW, Fawcett CR, Rathmell C, Tuck MWM. Process for the preparation of ethyl acetate. US Patent 6,809,217, Davy Process Technology Limited. 2004.Google Scholar
  23. 23.
    Yates M, Martı MJ, Casal B, Iglesias M, Esteban M, Ruiz-Hitzky E. Synthesis of p-cymene from limonene, a renewable feedstock. Appl Catal B Environ. 2008;81:218–24.CrossRefGoogle Scholar
  24. 24.
    Pace V, Hoyos P, Fernandez M, Sinisterra JV, Alcantara AR. 2-Methyltetrahydrofuran as a suitable green solvent for phthalimide functionalization promoted by supported KF. Green Chem. 2010;12:1380–2.CrossRefGoogle Scholar
  25. 25.
    Nardi M, Sindona G, Costanzo P, Oliverio M, Procopio A. Eco-friendly stereoselective reduction of α, β-unsaturated carbonyl compounds by Er(OTf)3/NaBH4 in 2-MeTHF. Tetrahedron. 2015;71:1132–5.CrossRefGoogle Scholar
  26. 26.
    Kumar P, Chandra V, Mani I. Dimethyl carbonate synthesis by transesterification of propylene carbonate with methanol: comparative assessment of Ce-M (M = Co, Fe, Cu, and Zn) catalysts. Renew Energy. 2016;88:3.CrossRefGoogle Scholar
  27. 27.
    Henderson RK, Jiménez-González C, Constable DJC, et al. Expanding GSK's solvent selection guide–embedding sustainability into solvent selection starting at medicinal chemistry. Green Chem. 2011;13:854–62.CrossRefGoogle Scholar
  28. 28.
    Hansen CM. The universality of the solubility parameter. Ind Eng Chem Prod Res Dev. 1969;8:2–11.CrossRefGoogle Scholar
  29. 29.
    Morrison WR, Smith LM. Preparation of fatty acid methyl esters and dimethylacetals from lipids with boron fluoride–methanol. J Lipid Res. 1964;5:600–8.Google Scholar
  30. 30.
    Ballabio DA. MATLAB toolbox for principal component analysis and unsupervised exploration of data structure. Chemom Intell Lab Syst. 2015;15:1–9.CrossRefGoogle Scholar
  31. 31.
    Muik B, Lendl B, Molina-Díaz A, Ayora-Cañada MJ. Direct monitoring of lipid oxidation in edible oils by Fourier transform Raman spectroscopy. Chem Phys Lipids. 2005;134:173–82.CrossRefGoogle Scholar
  32. 32.
    Vaskova H, Buckova M. Thermal degradation of vegetable oils: spectroscopic measurement and analysis. Procedia Eng. 2015;100:630–5.CrossRefGoogle Scholar
  33. 33.
    Kuligowski J, Quintás G, Garrigues S, de la Guardia M. Monitoring of polymerized triglycerides in deep-frying oil by on-line GPC-FTIR spectrometry using the science based calibration multivariate approach. Chromatographia. 2010;71:201–9.CrossRefGoogle Scholar
  34. 34.
    Loftsson T, Ilievska B, Asgrimsdottir GM, Ormarsson OT, Stefansson E. Fatty acids from marine lipids: biological activity, formulation, and stability. J Drug Deliv Sci Technol. 2013;34:71–5.CrossRefGoogle Scholar
  35. 35.
    Gertz C. Chemical and physical parameters as quality deep-frying process – changes at elevated temperature. Quality. 2000;102:566–72.Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2017

Authors and Affiliations

  • Mari Merce Cascant
    • 1
    • 2
  • Cassandra Breil
    • 1
  • Salvador Garrigues
    • 2
  • Miguel de la Guardia
    • 2
    Email author
  • Anne Silvie Fabiano-Tixier
    • 1
  • Farid Chemat
    • 1
    Email author
  1. 1.Université d’Avignon et des Pays de Vaucluse, INRA, UMR408, GREEN Team ExtractionAvignon CedexFrance
  2. 2.Department of Analytical ChemistryUniversity of ValenciaBurjassotSpain

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