Monoterpene separation by coupling proton transfer reaction time-of-flight mass spectrometry with fastGC

Materić, Dušan; Lanza, Matteo; Sulzer, Philipp; Herbig, Jens; Bruhn, Dan; Turner, Claire; Mason, Nigel and Gauci, Vincent (2015). Monoterpene separation by coupling proton transfer reaction time-of-flight mass spectrometry with fastGC. Analytical and Bioanalytical Chemistry, 407(25) pp. 7757–7763.

DOI: https://doi.org/10.1007/s00216-015-8942-5

Abstract

Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a well-established technique for real-time VOCs (Volatile Organic Compounds) analysis. Although, it is extremely sensitive (with sensitivities of up to 4500 cps/ppbv, limits of the detection < 1 pptv and the response times of approximately 100 ms) the selectivity of PTR-MS is still somewhat limited, as isomers cannot be separated. Recently, selectivity-enhancing measures, such as manipulation of drift tube parameters (reduced electric field strength) and using primary ions other than H₃O⁺, such as NO⁺ and O2⁺ have been introduced. However, monoterpenes, which belong to the most important plant VOCs, still cannot be distinguished so that more traditional technologies, such as gas chromatography mass spectrometry (GC-MS), have to be utilized. GC-MS is very time consuming (up to 1 h) and cannot be used for real-time analysis. Here we introduce a sensitive, near real-time method for plant monoterpene research: PTR-MS coupled with fastGC. We successfully separated and identified six of the most abundant monoterpenes in plant studies (α- and β-pinenes, limonene, 3-carene, camphene, and myrcene) in less than 80 s, using both standards and conifer branch enclosures (Norway spruce, Scots pine and Black pine). Five monoterpenes usually present in Norway spruce samples with a high abundance were separated even when the compound concentrations were diluted to 20 ppbv. Thus, fastGC-PTR-ToF-MS was shown to be an adequate one-instrument solution for plant monoterpene research.

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