The use of short columns, higher carrier gas velocity and fast temperature programs in Comprehensive Two-Dimensional Gas Chromatography coupled to Time-of- Flight Mass Spectrometry (GC x GC/TOFMS) technique is expected to increase the speed of analysis up to several orders of magnitude when compared to conventional gas chromatography (GC) or gas chromatography/mass spectrometry (GC/MS). A systematic evaluation of the GC x GC/TOFMS configuration for high-speed applications has received little attention in the literature. The feasibility of High Speed Comprehensive Two-Dimensional Gas Chromatography coupled to Mass Spectrometry (High speed GC x GC/MS) for complex mixtures has been investigated in this thesis. A particular focus was placed on comparing conventional scanning quadrupole mass spectrometry (qMS) with a newly available non-scanning time-of-flight instruments (TOFMS). Experiments were carried out using GC/qMS, GC x GC/qMS, GC/TOFMS and GC x GC/TOFMS both in normal (slow) and fast temperature rates coupled with high frequency modulation in GC x GC. Initially a complex mixture consists of 24 semivolatile compounds was used as the analyte for the above purpose. In the initial experiments parameters like acquisition rate and duty cycle for qMS were determined to evaluate the effectiveness of the instrument for fast analysis. The practical duty cycle value obtained for the qMS was only about 18 % for single ion and one compound at a dwell time of 10 ms in SIM mode. In both high-speed GC/qMS and high-speed GC x GC/qMS techniques only about 40 % of the components in the complex mixture were found to be well separated. The acquisition rate of scanning instruments like qMS is incompatible for fast eluting peaks in high speed GC. TOFMS that has an acquisition rate of several hundred spectra per second offer the potential to define the fast GC peaks accurately. The high quality spectra from TOFMS also enable deconvolution of coeluting peaks in the complex mixtures. The advantage of the automated spectral deconvolution is demonstrated for the identification of the coeluting peaks in the complex mixtures. Coelution of peaks is also observed with highspeed GC/TOFMS technique. The high-speed GC x GC/TOFMS was also tested with two different analyte system ??? A pesticide mixture and platformate (an aromatic mixture) to evaluate the suitability for high-speed analysis of complex mixtures. A poor resolution was observed for the pesticide mixture in the two-dimensional plane and it appeared, as there was nearly no orthogonal separation in the second dimension. The platformate mixture displayed a better two-dimensional separation. Chromatographic peak resolution is not really a primary requirement for locating and identifying the coeluting compounds in high-speed GC x GC/TOFMS technique. However, it was observed that the high-speed GC x GC/TOFMS too faced problem to unscramble the mass spectra of those compounds with similar structure and sharing the same unique masses.
| Identifer | oai:union.ndltd.org:ADTP/258066 |
| Date | January 2005 |
| Creators | Samiveloo, Silverraji, Chemistry, Faculty of Science, UNSW |
| Publisher | Awarded by:University of New South Wales. |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | Copyright Samiveloo Silverraji., http://unsworks.unsw.edu.au/copyright |
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