Thesis (MSc)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: This study focused on the potential of comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOF-MS) for the improved analysis of volatile wine constituents. Solid phase microextraction (SPME) in combination with GC×GC-TOF-MS was successfully used for the detailed investigation of the impact of three commercial Oenococcus oeni lactic acid bacteria (LAB) strains on the volatile composition of Pinotage wines subjected to malolactic fermentation (MLF). Due to increased separation power and enhanced sensitivity obtained by using two orthogonal separations coupled with the structural information provided by deconvoluted TOF-MS spectra, GC×GC-TOF-MS allowed for the identification and semi-quantitative analysis of much larger numbers of compounds compared to previous studies applying one-dimensional gas chromatography. The combination of univariate and multivariate statistical assessment was used as a powerful tool for data interpretation. The obtained results contribute significantly to the understanding of the impact of MLF on the volatile composition of Pinotage wine Some compounds have been linked to MLF for the first time. Moreover, the impact of these commercial starter cultures on the composition of volatile sulfur and nitrogen compounds in the same wines was studied by one-dimensional gas chromatographic methods with headspace injection and solid supported liquid-liquid extraction together with sulfur selective detection and tandem mass spectrometry. This study demonstrated also for the time, the impact of MLF on the composition of volatile sulfur and nitrogen compounds in Pinotage wine. GC×GC-TOF-MS was further used for the evaluation of the suitability of a new phase for stir bar sorptive extraction (SBSE) analysis of wine volatiles. Despite instrumental complications, beneficial extraction properties of the new stir bar phase for especially more polar compounds could be demonstrated. In addition, the extraction ability of this novel phase was evaluated for the analysis of selected thiazoles in wine using heart-cutting two dimensional gas chromatography in combination with nitrogen selective detection. Advantageous extraction performance of the new stir bar phase compared to a conventional polydimethylsiloxane (PDMS) phase for the determined thiazoles was demonstrated. / AFRIKAANSE OPSOMMING: Hierdie studie het gefokus daarop om die potensiaal van omvattende tweedimensionele gaschromatografie gekombineer met vlugtyd massaspektrometrie (GC×GC-TOF-MS) vir die verbeterde analise van vlugtige wynkomponente te ondersoek. Soliede fase mikro-ekstraksie (SPME) in kombinasie met GC×GC TOF MS is met sukses aangewend vir ‘n ondersoek na die impak van drie kommersiële Oenococcus oeni melksuur bakteria (LAB) rasse op die samestelling van die vlugtige fraksie van Pinotage wyne wat appelmelksuurgisting (AMG) ondergaan het. As gevolg van die verbeterde skeidingsvermoë en die verhoogte sensitiwiteit wat verkry word deur twee ortogonale skeidings te kombineer, tesame met die inligting aangaande die molekulêre struktuur wat die die gedekonvoleerde TOF massaspektra verskaf, maak GC×GC-TOF-MS die identifikasie en semi-kwantitatiewe analise van aansienlik meer komponente, in vergelyking met die gebruik van een-dimensionele gaschromatografie, moontlik. Die kombinasie van monoveranderlike asook multiveranderlike statistiese evaluering is gebruik as ‘n kragtige tegniek vir data interpretasie. Die resultate wat verkry is dra tot ‘n groot mate by tot die ontrafeling en begrip aangaande die impak wat AMG op die samestelling van vlugtige komponente in Pinotage wyn het. Daar word ook vir die eerste keer aangetoon dat somminge komponente verband te hou met AMG. Aanvullend hiertoe is die impak wat hierdie kommersiële kulture (wat gebruik word om fermentasie te inisieer) op die voorkoms van swawel en stikstof bevattende vlugtige komponente het bestudeer deur gebruik te maak van een-dimensionele gaschromatografiese metodes met ‘headspace’ inspuiting en vloeistof-voeistof ekstraksie tesame met swawel en stikstof selektiewe deteksie en tandem massaspektrometrie. Hierdie ondersoek werp lig, ook vir die eerste keer, op die samestelling van vlugtige swawel en stikstof bevattende komponente in Pinotage wyn. GC×GC-TOF-MS is ook gebruik vir die evalueering van die toepaslikheid van ‘n nuwe stasionêre fase vir gebruik met roerstaaf sorptiewe ekstraksie (SBSE) vir die analisering van vlugtige komponente in wyn. Ten spyte van instrumentele komplikasies, is die voordele wat hierdie nuwe fase vir die ekstraksie van vernaamlik meer polêre komponete aangetoon. Vervolgens is die ekstraksievermoë van hierdie nuwe fase vir die analise van sekere tiasole in wyn met ‘heart-cutting’ twedimensionaly gaschromatografie in kombinasie met stikstof-selektiewe deteksie gedemonstreer. Verbeterde ekstraksie van die nuwe roerstaaf fase vir die analise van tiasole, in vergelyking met ‘n tradisionele polydimethylsiloxane (PDMS) fase is voorts aangetoon.