Short communication Elucidation of the volatile composition of Marsala wines by using comprehensive two-dimensional gas chromatography Giacomo Dugo a , Flavio A. Franchina b , Maria R. Scandinaro a , Ivana Bonaccorsi b , Nicola Cicero a , Peter Q. Tranchida b,⇑ , Luigi Mondello b,c a Dipartimento di Scienze dell’Ambiente, della Sicurezza, del Territorio, degli Alimenti e della Salute (S.A.S.T.A.S.), Università di Messina, Viale Ferdinando d’Alcontres 31, 98166 Messina, Italy b Dipartimento di Scienze del Farmaco e dei Prodotti per la Salute, Università di Messina, Viale Annunziata, 98168 Messina, Italy c Centro Integrato di Ricerca (C.I.R.), Università Campus-Biomedico, Via Álvaro del Portillo, 21, 00128 Roma, Italy article info Article history: Received 28 March 2013 Received in revised form 9 July 2013 Accepted 12 July 2013 Available online 20 July 2013 Keywords: Marsala wine Comprehensive two-dimensional gas chromatography SPME Mass spectrometry Flame ionisation detector Volatiles abstract The present contribution describes a research work focused on the elucidation of the composition of the headspace of Marsala wine. Four sample-types, of different ageing (‘‘fine’’, ‘‘superiore secco’’, ‘‘superiore riserva’’, ‘‘vergine’’) were subjected to headspace solid-phase microextraction-comprehensive 2D GC analysis. At the outlet of the second GC dimension, the eluting analytes were split between a flame ionisation detector (for relative quantification purposes) and a rapid-scanning quadrupole mass spectrometer (for compound identification). Over 500 peaks were detected in each application, with a total of 128 compounds tentatively-identified considering the four sample types (mainly esters, alcohols, ketones, and aldehydes). The results attained open a door on the highly complex nature of the Marsala headspace; furthermore, they also demonstrated that the use of one-dimensional GC technologies, for the untargeted analysis of complex aroma profiles (e.g., dessert wines), is often too much of an analytical challenge. Ó 2013 Elsevier Ltd. All rights reserved. 1. Introduction Marsala wine, or simply ‘‘Marsala’’, is a well-known, highly appreciated and economically important dessert wine, produced exclusively in Sicily (Trapani province). Marsala is exported all over the world and is considered one of the four most important dessert wines together with Madeira, sherry and port. Marsala is charac- terised by an average alcoholic v/v content of 18%, and comes in three colours, namely ‘‘oro’’ (gold), ‘‘ambra’’ (amber) and ‘‘rubino’’ (ruby). The type of colour is dependent on the variety of grapes employed (Inzolia, Damaschino, Nerello Mascalese, etc.). Apart from colour, Marsala is classified by the degree of ageing and sugar content. Considering the former characteristic, Marsala can be: ‘‘fine’’ (above 1 year), ‘‘superiore’’ (above 2 years), ‘‘superior riser- va’’ (above 4 years), ‘‘vergine’’ (above 5 years), and ‘‘stravecchio’’ (above 10 years). With regards to the concentration of reducing sugars, the groups are: ‘‘secco’’ (below 40 g/L), ‘‘semi-secco’’ (be- tween 40 and 100 g/L), and ‘‘dolce’’ (above 100 g/L) (La Torre et al., 2008). In general, the consumption of foods and drinks is tightly related to the stimulation of the human senses, odour and taste. Food fla- vour, along with texture and appearance, has a fundamental impor- tance in the attraction of the consumer towards a particular food. With respect to odour, this sensation is generated by highly com- plex mixtures of volatile molecules (defined generically as aroma), in a variety of concentrations (Fisher & Scott, 1997). Currently, the analytical technique of choice for the untargeted elucidation of ar- oma profiles, in foods and drinks, is one-dimensional gas chroma- tography (1D-GC), hyphenated to a mass spectrometer (MS). It is obvious that GC–MS approaches can give qualitative (and possibly quantitative) information, but nothing on the odour sensation gen- erated by a specific analyte. Such important information can be at- tained through GC-olfactometry (GC-O) (d’Acampora Zellner et al., 2008). However, one of the main problems related to the 1D-GC analysis of aromas, with either MS and/or olfactometric detection, is that such samples are excessively complex for a single GC col- umn. The main consequence of insufficient separation power is that, often, compounds co-elute at the column outlet. The most suitable GC technique for the untargeted analysis of highly complex samples (>200 solutes) is comprehensive 2D-GC (GC Â GC), an approach introduced over twenty years ago (Liu & Phillips, 1991). GC Â GC analyses are usually carried out on a 0308-8146/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.foodchem.2013.07.061 ⇑ Corresponding author. Tel.: +39 090 6766510; fax: +39 090 358220. E-mail address: ptranchida@unime.it (P.Q. Tranchida). Food Chemistry 142 (2014) 262–268 Contents lists available at ScienceDirect Food Chemistry journal homepage: www.elsevier.com/locate/foodchem