Abstract
Abstract. Soft chemical ionization mass spectrometry (SCI-MS) techniques can be used to accurately quantify volatile organic compounds (VOCs) in air in real time; however, differentiation of isomers still represents a challenge. A suitable pre-separation technique is thus needed, ideally capable of analyses over a few tens of seconds. To this end, a bespoke fast gas chromatography (GC) instrument with an electrically heated 5 m long metallic capillary column was coupled to selected ion flow tube mass spectrometry (SIFT-MS) measurements. To assess the performance of this combination, a case study of monoterpene isomer (C10H16) analyses was carried out. The monoterpenes were quantified by SIFT-MS using H3O+ reagent ions (analyte ions C10H17+, m∕z 137, and C6H9+, m∕z 81) and NO+ reagent ions (analyte ions C10H16+, m∕z 136, and C7H9+, m∕z 93). The combinations of the fragment ion relative intensities obtained using H3O+ and NO+ were shown to be characteristic of the individual monoterpenes. Two non-polar GC columns (Restek Inc.) were tested: the advantage of MXT-1 was shorter retention, whilst the advantage of MXT-Volatiles was better separation. Thus, it is possible to identify components of a monoterpene mixture in less than 45 s using the MXT-1 column and to separate them in less than 180 s using the MXT-Volatiles column. Quality of the separation and the sensitivity of present technique (limit of detection, LOD, ∼16 ppbv) was found to be inferior compared to commercially available fast GC solutions coupled with proton transfer reaction mass spectrometry (PTR-MS, LOD ∼1 ppbv) due to the limited sample flow through the column. However, using combinations of two reagent ions improved identification of monoterpenes not well resolved by the chromatograms. As an illustrative example, the headspace of needle samples of three conifer species was analysed by both reagent ions and with both columns showing that mainly α-pinene, β-pinene and 3-carene were present. The system can thus be used for direct rapid monitoring of monoterpenes above 20 ppbv, such as applications in laboratory studies of monoterpene standards and leaf headspace analysis. Limitation of the sensitivity due to the total sample flow can be improved using a multi-column pre-separation.
Highlights
Monoterpenes, mostly emitted from plants, are very important biogenic volatile organic compounds (BVOCs) in the atmidaonsptshesurec.hDhuyedrtooxtyhleirrahdiigcahlsre(aOctHivqi)t,yowxiidthataiotmn oosfpmheornicotoexr--penes can lead to tropospheric ozone (O3) accumulation as well as secondary organic aerosol formation, which can affect human health and contribute to global climate change (Chameides et al, 1992; Fehsenfeld et al, 1992; Kulmala et al, 2004)
We report experimental developments aimed at selectively analysing individual monoterpenes in mixtures in air using a bespoke fast gas chromatography (GC) and selected ion flow tube mass spectrometry (SIFT-MS) combination with
To investigate if the various monoterpenes in a mixture could be effectively distinguished using SIFT-MS enhanced by the fast GC pre-separation, eight common biogenic monoterpenes were investigated
Summary
Monoterpenes, mostly emitted from plants, are very important biogenic volatile organic compounds (BVOCs) in the atmidaonsptshesurec.hDhuyedrtooxtyhleirrahdiigcahlsre(aOctHivqi)t,yowxiidthataiotmn oosfpmheornicotoexr--. Standard analytical methods used to identify and quantify volatile organic compounds (VOCs) in air, such as thermal desorption gas chromatography mass spectrometry The chemical ionization reactions that produced analyte ions are variously proton transfer, adduct ion formation, charge transfer and hydride ion transfer, principally depending on the type of reagent ions used This ion chemistry has been thoroughly reviewed in a number of publications (Smith and Španel, 2005). Standard SCI-MS techniques such as SIFT-MS and PTR-MS are limited to reporting concentrations of the sum of monoterpenes presented in the sample, and the composition of the monoterpenes present cannot be determined. SIFT-MS is widely used in VOCs analyses (Allardyce et al, 2006; Smith and Španel, analytical reaction c2o0n1d1itbio, n2s0a0n5db)t,hewHhi3cOh +h,aNs Ow+ella-nddefiOn+2edq reagent ions can be switched rapidly to analyse time-varying trace gas concentrations in air samples. This involved the analysis of both prepared laboratory monoterpene–air mixtures and the headspace of the foliage of different pine trees
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