Potential of selected ion flow tube mass spectrometry for real-time profiling of volatile malt aldehydes

JESSIKA DE CLIPPELEER (1), Filip Van Opstaele (1), Joeri Vercammen (2), Luc De Cooman (1), Guido Aerts (1)
(1) KaHo St.-Lieven, KULeuven Association, Laboratory of Enzyme, Fermentation, and Brewing Technology, Gent, Belgium; (2) Interscience BVBA, Interscience Expert Center, Louvain-la-Neuve, Belgium

Flavor stability remains one of the main quality criteria for beer, and the urgency to control it is endorsed by the global beer market and its allied need for longer storage times for exported beer. Formation and release of volatile aldehydes is recognized as one of the main causes of beer flavor deterioration upon storage. Most of these compounds pre-exist abundantly in malt, and may vary significantly between different malt types. As such, the staling potential of finished beer is largely determined by the type of malt used in the brewing process. Consequently, knowledge of malt aldehyde content is indispensable for brewers in view of quality control, selection of the appropriate malt variety, and objective assessment of the flavor stability of processed beer. The potential of selected ion flow tube mass spectrometry (SIFT-MS) to differentiate malted barley cultivars on the basis of their headspace profiles has been investigated in this study. Prime focus is on the analysis of aldehydes and particularly as compared to the headspace solid-phase microextraction (SPME) gas chromatography-MS method currently used. The investigated aldehyde markers can be classified into Strecker degradation aldehydes (2-methylpropanal, 2- and 3-methylbutanal, methional, benzaldehyde, and phenylacetaldehyde), aldehydes formed during Maillard reactions (furfural). and lipid oxidation aldehydes (hexanal and trans-2-nonenal). SIFT-MS is an analytical technique that is based upon soft chemical ionization taking place in a flow tube reactor. A commercial SIFT-MS instrument (Voice200, Syft Technologies, Christchurch, New Zealand) was equipped with a direct inlet and a heated external interface, which provided direct entry of volatiles into the flow tube. Volatile emissions from ungrounded malt grains were sampled with a micro-chamber/thermal extractor (µ-CTE; Markes International, Llantrisant, UK). Dynamic headspace with the µ-CTE uses a substantially higher amount of material (25 g). As a result, higher absolute responses are easily obtained without the need to increase extraction temperature and without inducing stress-related emissions. By dynamic headspace SIFT-MS, the target volatiles were readily identified in the different malt headspaces. The technique exhibited an increase in specificity and speed compared with the headspace SPME GC-MS procedure. The unique feature of SIFT-MS to analyze malt sample headspaces rapidly and directly without the need for sample preparation, derivatization, or chromatographic preseparation is demonstrated. Principal component analysis (PCA) was successfully applied to discriminate between malt samples on the basis of the selected aldehydes in their volatile pattern. Furthermore, PCA displayed good reproducibility of the SIFT analyses and showed the high potential of SIFT-MS for fast classification of the different malt samples investigated. Knowledge of these variations in headspace profiles among various malted barley types, varieties, and harvest years is of great interest to the brewing industry.

Jessika De Clippeleer obtained her M.S. degree in food technology, specialization food chemistry, from Wageningen University, The Netherlands, in 2003, after receiving an M.S. degree in industrial engineering in biochemistry at KaHo St.-Lieven, Gent, Belgium, in 2000, and studying at Escola Superior de Biotecnologia, Universidade Católica Portuguesa, Porto, Portugal, as an Erasmus student. She began employment with KaHo St.-Lieven in 2003 as a food chemist in the meat laboratory of the Biochemistry Department. In 2004 she joined the analytical laboratory of the Enzyme, Fermentation and Brewing Technology Research Group of KaHo St.-Lieven, where she started a Ph.D. study on beer flavor stability and hopping technology in 2005. In addition to her Ph.D. research activities, she is involved in several research projects and lectures on biochemistry and food safety. Her research experience is in the field of food chemistry, beer flavor stability, hop chemistry, and malting. Her expertise is in principles, technology, and applications of analytical chromatographic and mass spectrometric techniques.

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