Rapid Plant Volatiles Screening Using Headspace SPME and Person-Portable Gas Chromatography–Mass Spectrometry


Rapid on-site screening of biogenic volatile emissions from leaves of living plants is demonstrated, using headspace solid-phase microextraction (HS-SPME) with a portable gas chromatograph (PGC), fitted with a low-thermal mass (LTM) column equipped with a miniature toroidal ion trap mass spectrometer (ITMS). For field sampling, the study was conducted at the Royal Botanical Garden, Cranbourne, Australia, with the sampling site located in the Peppermint Garden. Twelve designated plants in the families of Asteraceae, Lamiaceae, Myrtaceae, Pittosporaceae, and Rutaceae were chosen for this field study. A customised SPME syringe was used for headspace sampling and sample introduction; leaves were collected into vials, equilibrated, sampled onto a PDMS/DVB-coated fibre, then desorbed in the GC inlet in split mode. A resistively heated LTM, narrow bore (0.1 mm ID) non-polar capillary column heated at 2 °C s−1 to 270 °C, provided fast GC elution with total run time of 3 min. The miniaturised ITMS was operated over a mass range of 40–500 Da. This provided approximation of near-real-time measurement of leaf volatiles released from the plant. For a second study, PGC–ITMS is employed to profile essential oils from experimental hybrid and commercial Humulus lupulus L. (hop) plant extracts in the laboratory, and contrasted with bench-top data. Results were processed by chromatographic fingerprinting using retention times, and MS fragmentation pattern similarity criteria. Unsupervised multivariate analysis was performed to improve specificity for classification of different plant volatiles, yielding loading variables corresponding to chemical differences of the analysed plants. The combination of HS-SPME and portable GC–ITMS proved effective for rapid chemical expression of the plant volatile genotype in the field.

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  1. 1.

    Maffei ME, Gertsch J, Appendino G (2011) Plant volatiles: production, function and pharmacology. ‎Nat Prod Rep 28:1359–1380

    Article  CAS  PubMed  Google Scholar 

  2. 2.

    Dudareva N, Pichersky E (2008) Metabolic engineering of plant volatiles. Curr Opin Biotechnol 19:181–189

    Article  CAS  PubMed  Google Scholar 

  3. 3.

    Lerdau M, Guenther A, Monson R (1997) Plant production and emission of volatile organic compounds. Bioscience 47:373–383

    Article  Google Scholar 

  4. 4.

    Fall R, Karl T, Hansel A, Jordan A, Lindinger W (1999) Volatile organic compounds emitted after leaf wounding: on-line analysis by proton-transfer-reaction mass spectrometry. J Geophys Res Atmos 104:15963–15974

    Article  CAS  Google Scholar 

  5. 5.

    Holopainen JK, Gershenzon J (2010) Multiple stress factors and the emission of plant VOCs. Trends Plant Sci 15:176–184

    Article  CAS  PubMed  Google Scholar 

  6. 6.

    Zhang Z, Li G (2010) A review of advances and new developments in the analysis of biological volatile organic compounds. Microchem J 95:127–139

    Article  CAS  Google Scholar 

  7. 7.

    Liu X, Nacson S, Grigoriev A, Lynds P, Pawliszyn J (2006) A new thermal desorption solid-phase microextraction system for hand-held ion mobility spectrometry. Anal Chim Acta 559:159–165

    Article  CAS  Google Scholar 

  8. 8.

    Malcolm A, Wright S, Syms RRA, Dash N, Schwab M-A, Finlay A (2010) Miniature mass spectrometer systems based on a microengineered quadrupole filter. Anal Chem 82:1751–1758

    Article  CAS  PubMed  Google Scholar 

  9. 9.

    Contreras JA, Murray JA, Tolley SE, Oliphant JL, Tolley HD, Lammert SA, Lee ED, Later DW, Lee ML (2008) Hand-portable gas chromatograph-toroidal ion trap mass spectrometer (GC-TMS) for detection of hazardous compounds. J Am Soc Mass Spectrom 19:1425–1434

    Article  CAS  PubMed  Google Scholar 

  10. 10.

    Smith PA, Lepage CRJ, Savage PB, Bowerbank CR, Lee ED, Lukacs MJ (2011) Use of a hand-portable gas chromatograph–toroidal ion trap mass spectrometer for self-chemical ionization identification of degradation products related to O-ethyl S-(2-diisopropylaminoethyl) methyl phosphonothiolate (VX). Anal Chim Acta 690:215–220

    Article  CAS  PubMed  Google Scholar 

  11. 11.

    Barreira LMF, Parshintsev J, KÓ“rkkÓ“inen N, Hartonen K, Jussila M, Kajos M, Kulmala M, Riekkola M-L (2015) Field measurements of biogenic volatile organic compounds in the atmosphere by dynamic solid-phase microextraction and portable gas chromatography–mass spectrometry. Atmos Environ 115:214–222

    Article  CAS  Google Scholar 

  12. 12.

    Syage JA, Nies BJ, Evans MD, Hanold KA (2001) Field-portable, high-speed GC/TOFMS. J Am Soc Mass Spectrom 12:648–655

    Article  CAS  PubMed  Google Scholar 

  13. 13.

    Wang A, Tolley HD, Lee ML (2012) Gas chromatography using resistive heating technology. J Chromatogr A 1261:46–57

    Article  CAS  PubMed  Google Scholar 

  14. 14.

    Smith PA (2012) Person-portable gas chromatography: rapid temperature program operation through resistive heating of columns with inherently low thermal mass properties. J Chromatogr A 1261:37–45

    Article  CAS  PubMed  Google Scholar 

  15. 15.

    Ras MR, Borrull F, Marce RM (2009) Sampling and preconcentration techniques for determination of volatile organic compounds in air samples. Trends Anal Chem 28:347–361

    Article  CAS  Google Scholar 

  16. 16.

    Kralj D, Zupanec J, Vasilj D, Kralj S, Pšeničnik J (1991) Variability of essential oils of hops, Humulus lupulus L. J Inst Brew 97:197–206

    Article  CAS  Google Scholar 

  17. 17.

    Kovačevič M, Kač M (2002) Determination and verification of hop varieties by analysis of essential oils. Food Chem 77:489–494

    Article  Google Scholar 

  18. 18.

    Dresel M, Vogt C, Dunkel A, Hofmann T (2016) The bitter chemodiversity of Hops (Humulus lupulus L.). J Agric Food Chem 64:7789–7799

    Article  CAS  PubMed  Google Scholar 

  19. 19.

    Eyres GT, Marriott PJ, Dufour JP (2007) Comparison of odor-active compounds in the spicy fraction of hop (Humulus lupulus L.) essential oil from four different varieties. J Agric Food Chem 55:6252–6261

    Article  CAS  PubMed  Google Scholar 

  20. 20.

    Van Opstaele F, De Causmaecker B, Aerts G, De Cooman L (2012) Characterization of novel varietal floral hop aromas by headspace solid phase microextraction and gas chromatography–mass spectrometry/olfactometry. J Agric Food Chem 60:12270–12281

    Article  CAS  PubMed  Google Scholar 

  21. 21.

    Luong J, Gras R, Mustacich R, Cortes H (2006) Low thermal mass gas chromatography: principles and applications. J Chromatogr Sci 44:253–261

    Article  CAS  PubMed  Google Scholar 

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DDY gratefully acknowledges the provision of a Tasmania Graduate Research Scholarship. The authors also thank PerkinElmer for providing the ppGC–ITMS system used in this study. The authors acknowledge University of Messina for support through the “Research and Mobility” collaborative project.

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Correspondence to Philip J. Marriott.

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Published in Chromatographia’s 50th Anniversary Commemorative Issue.

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Wong, Y.F., Yan, D., Shellie, R.A. et al. Rapid Plant Volatiles Screening Using Headspace SPME and Person-Portable Gas Chromatography–Mass Spectrometry. Chromatographia 82, 297–305 (2019). https://doi.org/10.1007/s10337-018-3605-2

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  • Low-thermal mass gas chromatography
  • Portable mass spectrometry
  • Leaf volatiles
  • Hop essential oils
  • On-site analysis