Addition of fast gas chromatography to selected ion flow tube mass spectrometry for analysis of individual monoterpenes in mixtures

0511863 - ÚFCH JH 2020 RIV DE eng J - Journal Article
Lacko, Michal - Wang, N. - Sovová, Kristýna - Pásztor, Pavel - Španěl, Patrik
Addition of fast gas chromatography to selected ion flow tube mass spectrometry for analysis of individual monoterpenes in mixtures.
Atmospheric Measurement Techniques. Roč. 12, č. 9 (2019), s. 4965-4982. ISSN 1867-1381. E-ISSN 1867-8548
R&D Projects: GA ČR(CZ) GJ17-13157Y
EU Projects: European Commission(XE) 674911 - IMPACT
Institutional support: RVO:61388955
Keywords : volatile organic-compounds * ptr-ms measurements * phase reactions * rate constants * scots pine * humid air * sift-ms * no+ * emissions * h3o+
OECD category: Physical chemistry
Impact factor: 3.668, year: 2019
Method of publishing: Open access

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 5m 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, similar to 16 ppbv) was found to be inferior compared to commercially available fast GC solutions coupled with proton transfer reaction mass spectrometry (PTR-MS, LOD similar to 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 alpha-pinene, beta-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.
Permanent Link: http://hdl.handle.net/11104/0302112