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Stable isotope dilution analysis of wine fermentation products by HS-SPME-GC-MS

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Abstract

The aim of this study was to quantify, in a single analysis, 31 volatile fermentation-derived products that contribute to the aroma of red and white wine. We developed a multi-component method based on headspace solid-phase microextraction coupled with gas chromatography mass spectrometry (HS-SPME-GC-MS). The 31 volatile compounds analysed include ethyl esters, acetates, acids and alcohols. Although these compounds have a range of functional groups, chemical properties, volatilities, affinities for the SPME fibre, and are found in wine at various concentrations, the accuracy of the analysis was achieved with the use of polydeuterated internal standards for stable isotope dilution analyses (SIDA). Nine of the labelled standards were commercially available, while 22 were synthesised. The method was validated by a series of duplicate spiked standard additions to model, white and red wine matrices over the concentration range relevant for each compound in wine. This demonstrated that the appropriate use of SIDA helped to account for matrix effects, for instance potential sources of variation such as the relative response to the MS detector, ionic strength, ethanol content and pH of different wine matrices. The resultant calibration functions had correlation coefficients (R2) ranging from 0.995 to 1.000. Each compound could be quantified at levels below its aroma threshold in wine. Relative standard deviations were all <5%. The method was optimised for the best compromise (over the 31 compounds) of wine dilution factor, level of sodium chloride addition, SPME fibre, SPME temperature, SPME time, GC column and MS conditions. Confirmation of identity was achieved by retention time and peak shape, and measurement of at least three ions for each analyte and internal standard with the MS operating in selected ion monitoring mode to facilitate more precise quantitation with a high sampling rate. The method is a valuable research tool with many relevant applications. A novel method for the combined chiral separation and SIDA quantification of 2- and 3-methylbutanoic acid is also demonstrated.

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Acknowledgments

Kate Howell is acknowledged for her work in the preliminary development and validation of methodology for the analysis of the acetates at the Australian Wine Research Institute (AWRI). We thank Gordon Elsey of the AWRI for his expertise with NMR. Jose Newton is thanked for her technical assistance distilling labelled standards. We thank Peter Winterhalter (Institute of Food Chemistry, Technical University of Braunschweig) and Sakkie Pretorius, Peter Høj and Leigh Francis of the AWRI for valued discussions and encouragement. This project is supported by Australia’s grapegrowers and winemakers through their investment body the Grape and Wine Research and Development Corporation, with matching funds from the Australian Government, under projects AWR2 and AWR6, and by the Commonwealth Cooperative Research Centres Program of Australia.

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Authors and Affiliations

  1. The Australian Wine Research Institute, P.O. Box 197, Glen Osmond (Adelaide), SA, 5064, Australia

    Tracey E. Siebert, Heather E. Smyth, Dimitra L. Capone, Corinna Neuwöhner, Kevin H. Pardon, George K. Skouroumounis, Markus J. Herderich, Mark A. Sefton & Alan P. Pollnitz

  2. Cooperative Research Centre for Viticulture, P.O. Box 154, Glen Osmond (Adelaide), SA, 5064, Australia

    Tracey E. Siebert, Heather E. Smyth, Dimitra L. Capone, Kevin H. Pardon, George K. Skouroumounis, Markus J. Herderich, Mark A. Sefton & Alan P. Pollnitz

  3. School of Agriculture and Wine, The University of Adelaide, Waite Campus, Glen Osmond (Adelaide), SA, 5064, Australia

    Heather E. Smyth, Markus J. Herderich & Mark A. Sefton

  4. Institute of Food Chemistry, Technical University of Braunschweig, Schleinitzstrasse 20, 38106, Braunschweig, Germany

    Corinna Neuwöhner

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  1. Tracey E. Siebert
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  9. Alan P. Pollnitz
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Correspondence to Alan P. Pollnitz.

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Siebert, T.E., Smyth, H.E., Capone, D.L. et al. Stable isotope dilution analysis of wine fermentation products by HS-SPME-GC-MS. Anal Bioanal Chem 381, 937–947 (2005). https://doi.org/10.1007/s00216-004-2992-4

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  • DOI: https://doi.org/10.1007/s00216-004-2992-4

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