Optimization of a Solid-Phase Microextraction method for the Gas Chromatography–Mass Spectrometry analysis of blackberry (Rubus ulmifolius Schott) fruit volatiles

A Solid-Phase Microextraction method for the Gas Chromatography–Mass Spectrometry analysis of blackberry (Rubus sp.) volatiles has been fully optimized by means of a Box–Behnken experimental design. The optimized operating conditions (Carboxen/Polydimethylsiloxane fiber coating, 66 °C, 20 min equilibrium time and 16 min extraction time) have been applied to the characterization for the first time of the volatile composition of Rubus ulmifolius Schott blackberries collected in Italy and Spain. A total of 74 volatiles of different functionality were identified; esters and aliphatic alcohols were the predominant classes in both sample types. Methylbutanal (2.02–25.70%), ethanol (9.84–68.21%), 2,3-butanedione (2.31–14.71%), trans-2-hexenal (0.49–17.49%), 3-hydroxy-2-butanone (0.08–7.39%), 1-hexanol (0.56–16.39%), 1-octanol (0.49–10.86%) and methylbutanoic acid (0.53–21.48%) were the major compounds in most blackberries analyzed. Stepwise multiple regression analysis of semiquantitative data showed that only two variables (ethyl decanoate and ethyl acetate) were necessary for a successful differentiation of blackberries according to their harvest location.