Abstract
Introduction. Like any other food product, alcoholic drinks are subject to falsification. The present research featured various methods of analysis that can be applied to control the quality and authenticity of wine production. In case of doubt, experts apply national and interstate standards, the most informative of which are based on the isotopic mass spectrometry principle. Fruit winemaking relies on beet or cane sugar. Researchers have to develop a method to identify the difference between conditionally exogenous alcohols, which are formed during fermentation, and real exogenous alcohols, introduced in the form of rectified ethyl alcohol of grain origin. In order to identify non-grape alcohol, experts measure the ratio of ethanol carbon isotopes in the wine. However, δ13C‰ alone is not sufficient to analyze fruit wines and other alcohol drinks. Ratios of 18O/16O and D/H isotopes can become an extra criterion to test the authenticity of fruit table wines.Study objects and methods. The mass spectrometric complex Delta V Advantage Thermo Fisher Scientific (USA) provided a precise analysis of 13C/12C, 18O/16O, D/H isotopes. Wine samples were prepared in laboratory conditions from six types of fruits: apples, pears, cherries, black currants, plums, and chokeberries. Apple wine was obtained from fermented wort; other samples were fermented from pulp. Fermentation temperature was 20 ± 2°C, while the yeast race was represented by Vishnyovaya 33.
Results and discussion. In fruit wine production, grain ethanol is the most popular falsification tool: it increases alcohol content instead of sugar, and sometimes even without fermentation process. In this regard, the research focused on carbon, oxygen, and grain alcohols hydrogen isotope characteristics, as well as fruit wines, obtained as a result of technology violation. The fruit wine alcohol mixes developed from joint fermentation of fruit sugars and introduced sugary substances. Cane sugar, beet sugar, and corn glucose and fructose syrup were added to the wort or pulp to establish the isotopic characteristics of the mix. The rate of exogenous alcohol production was 5% by volume.
Conclusion. The analysis of δ13C‰ indicator failed to detect introduced grain alcohol. The analysis of isotopes of all atoms in the ethanol molecule, namely carbon, oxygen, and hydrogen, proved to be much more effective. The introduction of sugary substances prior to or during fruit juice fermentation provided the required alcohol content. It also reduced the numerical value of δ18O‰ of ethanol, which makes it significantly different from that of fortified fruit wines obtained by introducing grain alcohol into fermented fruit juice. Thus, the δD‰ indicator can serve as an additional criterion in order to identify possible violations of technological process of fruit table wines production.
Keywords
Alcohol, fruit wines, isotopes, carbon, oxygen, hydrogen, mass spectrometry, adulteration, fermentationREFERENCES
- Yakuba YuF, Kaunova AA, Temerdashev ZA, Titarenko VO, Halafjan AA. Grape wines, problems of their quality and regional origin evaluation. Analytics and Control. 2014;18(4):344–372. (In Russ.).
- Lelova Z, Ivanova-Petropulos V, Masár M, Lisjak K, Bodor R. Optimization and validation of a new capillary electrophoresis method with conductivity detection for determination of small anions in red wines. Food Analytical Methods. 2018;11(5):1457–1466. https://doi.org/10.1007/s12161-017-1117-6.
- Pereira V, Câmara JS, Cacho J, Marques JC. HPLC-DAD methodology for the quantification of organic acids, furans and polyphenols by direct injection of wine samples. Journal of Separation Science. 2010;33(9):1204–1215. https://doi.org/10.1002/jssc.200900784.
- Regmi U, Palma M, Barroso CG. Direct determination of organic acids in wine and wine-derived products by Fourier transform infrared (FT-IR) spectroscopy and chemometric techniques. Analytica Chimica Acta. 2012;732:137–144. https://doi.org/10.1016/j.aca.2011.11.009.
- Baffi C, Trincherini PR. Food traceability using the 87Sr/86Sr isotopic ratio mass spectrometry. European Food Research and Technology. 2016;242(9):1411–1439. https://doi.org/10.1007/s00217-016-2712-2.
- Silva FLN, Schmidt EM, Messias CL, Eberlin MN, Sawaya ACHF. Quantitation of organic acids in wine and grapes by direct infusion electrospray ionization mass spectrometry. Analytical Methods. 2015;7(1):53–62. https://doi.org/10.1039/c4ay00114a.
- Jacobson D, Monforte AR, Ferreira ACS. Untangling the chemistry of port wine aging with the use of GC-FID, multivariate statistics, and network reconstruction. Journal of Agricultural and Food Chemistry. 2013;61(10):2513–2521. https://doi.org/10.1021/jf3046544.
- Mayr CM, Capone DL, Pardon KH, Black CA, Pomeroy D, Francis IL. Quantitative analysis by GC-MS/MS of 18 aroma compounds related to oxidative off-flavor in wines. Journal of Agricultural and Food Chemistry. 2015;63(13):3394–3401. https://doi.org/10.1021/jf505803u.
- Cunha SC, Faria MA, Fernandes JO. Gas chromatography-mass spectrometry assessment of amines in port wine and grape juice after fast chloroformate extraction/derivatization. Journal of Agricultural and Food Chemistry. 2011;59(16):8742–8753. https://doi.org/10.1021/jf201379x.
- Kushnereva EV, Guguchkina TI, Pankin MI, Lopatina LM. Mathematical modeling of dependences of quality of table wines from physical and chemical indicators. Winemaking and Viticulture. 2011;(4):18–21. (In Russ.).
- Camin F, Bontempo L, Perini M, Tonon A, Breas O, Guillou C, et al. Food Control. 2013;29(1):107–111. https://doi.org/10.1016/j.foodcont.2012.05.055.
- Spangenberg JE, Zufferey V. Carbon isotope compositions of whole wine, wine solid residue, and wine ethanol, determined by EA/IRMS and GC/C/IRMS, can record the vine water status – a comparative reappraisal. Analytical and Bioanalytical Chemistry. 2019;411(10):2031–2043. https://doi.org/10.1007/s00216-019-01625-4.
- Dutra SV, Adami L, Marcon AR, Carnieli GJ, Roani CA, Spinelli FR, et al. Characterization of wines according the geographical origin by analysis of isotopes and minerals and the influence of harvest on isotope values. Food Chemistry. 2013;141(3):2148–2153. https://doi.org/10.1016/j.foodchem.2013.04.106.
- Cheng J, Zhai Y, Taylor DK. Several mineral elements discriminate the origin of wines from three districts in China. International Journal of Food Properties. 2015;18(7):1460–1470. https://doi.org/10.1080/10942912.2014.903415.
- Oganesyants LA, Panasyuk AL, Kuzmina EI, Kharlamova LN. Determination of the carbon isotope 13C/12C in ethanol of fruit wines in order to define identification characteristics. Foods and Raw Materials. 2016;4(1):141–147. https://doi.org/10.21179/2308-4057-2016-1-141-147.
- Christoph N, Hermann A, Wachter H. 25 Years authentication of wine with stable isotope analysis in the European Union – Review and outlook. BIO Web of Conferences. 2015;5. https://doi.org/10.1051/bioconf/20150502020.
- Winterová R, Mikulíková R, Mazáč J, Havelec P. Assessment of the authenticity of fruit spirits by gas chromatography and stable isotope ratio analyses. Czech Journal of Food Sciences. 2008;26(5):368–375. https://doi.org/10.17221/1610-cjfs.
- Oganesyantc LA, Panasyuk AL, Kuzmina EI, Zyakun AM. Isotopic features of ethanol of the Russian grape wine. Winemaking and Viticulture. 2015;(4):8–13. (In Russ.).
- Obnaruzhenie obogashcheniya susla, kontsentrirovannogo susla, vinogradnogo sakhara i vin s primeneniem yadernogo magnitnogo rezonansa deyteriya (RMN-FINS) [Detection of enrichment of musts, concentrated musts, grape sugar and wines by application of deuterium nuclear magnetic resonance (RMN-FINS)]. Sbornik mezhdunarodnykh metodov analiza vin i susla [Collection of international methods for the analysis of wines and must]. 2017. (In French).
- Opredelenie raspredeleniya deyteriya v ehtanole v spirtnykh napitkakh vinodelʹcheskogo proiskhozhdeniya s pomoshchʹyu yadernogo magnitnogo rezonansa deyteriya [Determination of the distribution of deuterium in ethanol in spirit drinks of vitivinicultural origin by application of nuclear magnetic resonance of deuterium]. Sbornik mezhdunarodnykh metodov analiza vin i susla [Collection of international methods for the analysis of wines and must]. 2017. (In French).