Development of a methodology based on headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry for the analysis of esters in brandies.

[Display omitted] • A method for ester determination in brandies was developed. • Response surface methodology (RSM) was used for HS-SPME optimization. • A desirability function allowed to optimize multiple metabolite responses. • The method developed was used to characterize the ester profile of sherry brandies. • Differences in the ester profile related to the ageing of brandies were revealed. A specific method for the simultaneous quantification of 28 esters in brandies using headspace solid-phase microextraction and gas-chromatography coupled to mass spectrometry (HS-SPME-GC–MS) was optimised and validated. First, the optimal extraction conditions were determined by using response surface methodology, which were obtained for an extraction temperature of 33 °C for 55 min and a sample dilution of 7.2 % v/v ethanol. Eight deuterated ethyl esters were used as internal standards to provide specificity for the method, which was successfully validated in terms of linearity (R2 > 0.981), repeatability (1 % < RSD < 30 %), reproducibility (1 % < RSD < 18 %), sensitivity (1.1 μg/L < LOQ < 1878 μg/L), accuracy (81 % < recovery < 118 %), and matrix effect. Then, the optimised method was tested on Spanish sherry brandies matured through the traditional dynamic ageing system of Criaderas and Solera , observing an overall decrease in most of the esters during their first years of ageing, although an increase in ethyl esters of branched acids was found. These results confirmed the suitability of the developed method for the determination of esters in brandies and provide the basis for further studies on brandy esters. [ABSTRACT FROM AUTHOR]