Improvement of a headspace solid phase microextraction-gas chromatography/mass spectrometry method for the analysis of wheat bread volatile compounds

•A semi-quantitative HS-SPME/GC-MS method for bread volatiles was improved.•A number of 39 volatiles were fully identified, while 95 volatiles were tentatively identified.•Method precision was improved by using an array of ten internal standards.•Method linearity was verified in matrix-matched extraction solutions.•This method may prove useful when studying aroma formation in bakery products.

An improved method based on headspace solid phase microextraction combined with gas chromatography–mass spectrometry (HS-SPME/GC–MS) was proposed for the semi-quantitative determination of wheat bread volatile compounds isolated from both whole slice and crust samples. A DVB/CAR/PDMS fibre was used to extract volatiles from the headspace of a bread powdered sample dispersed in a sodium chloride (20%) aqueous solution and kept for 60 min at 50 °C under controlled stirring. Thirty-nine out of all the extracted volatiles were fully identified, whereas for 95 other volatiles a tentative identification was proposed, to give a complete as possible profile of wheat bread volatile compounds. The use of an array of ten structurally and physicochemically similar internal standards allowed to markedly improve method precision with respect to previous HS-SPME/GC–MS methods for bread volatiles. Good linearity of the method was verified for a selection of volatiles from several chemical groups by calibration with matrix-matched extraction solutions. This simple, rapid, precise and sensitive method could represent a valuable tool to obtain semi-quantitative information when investigating the influence of technological factors on volatiles formation in wheat bread and other bakery products.