Analytica Chimica Acta 770 (2013) 1–6 Contents lists available at SciVerse ScienceDirect Analytica Chimica Acta j ourna l ho me page: www.elsevier.com/locate/aca Multiple headspace-solid-phase microextraction: An application to quantification of mushroom volatiles Rosaria Costa a , Laura Tedone a , Selenia De Grazia a , Paola Dugo a,b , Luigi Mondello a,b,∗ a Dipartimento Farmaco-chimico, University of Messina, viale Annunziata, 98168 Messina, Italy b Centro Integrato di Ricerca (C.I.R.), Università Campus-Biomedico, Via Álvaro del Portillo, 21, 00128 Roma, Italy h i g h l i g h t s ◮ Multiple headspace extraction-solid phase microextraction (MHS-SPME) has been applied to the analysis of Agaricus bisporus. ◮ Mushroom flavor is characterized by the presence of compounds with a 8- carbon atoms skeleton. ◮ Formation of 8-carbon compounds involves a unique fungal biochemical pathway. ◮ The MHS-SPME allowed to deter- mine quantitatively 5 target analytes of A. bisporus for the first time. g r a p h i c a l a b s t r a c t a r t i c l e i n f o Article history: Received 26 November 2012 Received in revised form 17 January 2013 Accepted 20 January 2013 Available online 6 February 2013 Keywords: Multiple headspace extraction Solid phase microextraction Mushroom flavor Agaricus bisporus Quantitative analysis a b s t r a c t Multiple headspace-solid phase microextraction (MHS-SPME) followed by gas chromatography/mass spectrometry (GC–MS) and flame ionization detection (GC–FID) was applied to the identification and quantification of volatiles released by the mushroom Agaricus bisporus, also known as champignon. MHS- SPME allows to perform quantitative analysis of volatiles from solid matrices, free of matrix interferences. Samples analyzed were fresh mushrooms (chopped and homogenized) and mushroom-containing food dressings. 1-Octen-3-ol, 3-octanol, 3-octanone, 1-octen-3-one and benzaldehyde were common con- stituents of the samples analyzed. Method performance has been tested through the evaluation of limit of detection (LoD, range 0.033–0.078 ng), limit of quantification (LoQ, range 0.111–0.259 ng) and ana- lyte recovery (92.3–108.5%). The results obtained showed quantitative differences among the samples, which can be attributed to critical factors, such as the degree of cell damage upon sample preparation, that are here discussed. Considerations on the mushrooms biochemistry and on the basic principles of MHS analysis are also presented. © 2013 Elsevier B.V. All rights reserved. 1. Introduction Solid-phase microextraction is a well established sample prepa- ration technique that has gained an enormous success during the years, dating back to more than 20 years ago. From the pioneer ∗ Corresponding author at: Dipartimento Farmaco-chimico, University of Messina, viale Annunziata, 98168 Messina, Italy. Tel.: +39 090 6766536; fax: +39 090 358220. E-mail address: lmondello@unime.it (L. Mondello). works by Pawliszyn and co-workers published in 1992, the num- ber of publications has grown exponentially up to around 1084 papers, based on the use of SPME, in 2011 [1]. SPME is easy, fast, simple, convenient, and environmentally friendly. However, one of the features of this technique, which turns to be at the same time a drawback, is that SPME performs a non-exhaustive extraction. In SPME, the process of extraction is based on the achievement of equilibria between sample matrix and headspace, and between headspace and fiber coating. A SPME extraction is considered com- plete when the equilibria are established, although this phase doesn’t correspond necessarily to the exhaustion of analytes from 0003-2670/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.aca.2013.01.041