Abstract

Flavorings give commercial alcoholic beverages a recognizable sensory profile. Their quality, chemical composition, acceptable levels, and control methods are standardized by the state. For home-made alcoholic beverages, the market offers a wide range of flavorings that imitate popular brands. However, their composition is seldom labelled, and their quality control methods remain unknown. The research objective was to study the component composition of imitation flavorings in order to develop appropriate analytical measurement protocols. The research featured flavorings of different brands that imitate flavor profiles of cognac, chacha, tequila, brandy, gin, and liqueur. It included a FT-801 Fourier spectrometer (SPF SIMEX, Russia) with SIMEX attachment (Russia) for attenuated total internal reflectance, as well as a Crystal-5000.2 gas chromatograph (Russia) with a TR-5MS column and an ISQ quadrupole mass spectrometric detector (Thermo Fisher Scientific, USA). To detect the solvents (carriers), 0.050 cm3 of each sample solution was mixed with 10 cm3 of methanol. To detect the flavoring agent, the sample solutions were pre-extracted with trichloromethane (chloroform). The obtained IR-NIR spectra were processed using the OMNIC software; the mass spectra were processed with NIST MS Search 2.0 (NIST, USA). The research revealed the following data on the nature of solvent carriers and flavoring agents. Propylene glycol, glycerol, and triacetin acted as solvents (carriers). As few as 1-5 substances were responsible for the sensory profile, but they made up ≥ 70% of the total composition. The cognac flavoring of the Elix brand contained 4-hydroxy-3-methoxybenzaldehyde (vanillin, 78.5%); the chacha flavor (Alcotec) was provided by 3,7-dimethyl-1,6-octadien-3-ol and methyl-2-aminobenzoate (94.4%); the brandy taste (Alcotec) was imitated by vanillin and ethyl laurate (81.7%); the tequila flavoring (Alcostar) contained 3-methyl-1-butanol, ethyl decanoate, ethyl laurate, and vanillin (73.7%); the gin-tonic flavor (Etol) resulted from a combination of phenylmethanol, 3,7-dimethyl-1,6-octadien-3-ol, (1R)-1-isopropyl-4-methyl-3-cyclohexen-1-ol, and 2-(4-methyl-3-cyclohexen-1-yl)-2-propanol (83.5%). None of the artificial additives had the same flavoring agents in the same relative content as the original drinks. In this study, a combination of FTIR-ATR spectrometry and GC-MS spectrometry with subsequent mathematical processing provided comprehensive information on the chemical composition of flavoring agents that could be used to assess their sensory profiles, food safety, and authenticity.

Keywords

Alcoholic beverages, flavoring agent, food additives, FTIR-ATR, GC-MS, chemometrics

REFERENCES

1. de Castilhos MBM, de Queiroga APG, Sabino LL, dos Santos JR, Santiago UA, et al. Flavor biochemistry of fermented alcoholic beverages. In: Gopi S, Sukumaran NP, Jacob J, Thomas S, editors. Natural Flavours, Fragrances, and Perfumes: Chemistry, Production, and Sensory Approach. Berlin: Wiley-VCH GmbH; 2023, pp. 91–114. https://doi.org/10.1002/9783527824816.ch6
2. Wu J, Liu Y, Zhao H, Huang M, Sun Y, et al. Recent advances in the understanding of off-flavors in alcoholic beverages: Generation, regulation, and challenges. Journal of Food Composition and Analysis. 2021;103:104117. https://doi.org/ 10.1016/j.jfca.2021.104117
3. Yan Q, Zhang K, Zou W, Hou Y. Three main flavour types of Chinese Baijiu: Characteristics, research, and perspectives. Journal of the Institute of Brewing. 2021;127(4):317–326. https://doi.org/10.1002/jib.669
4. Daute M, Jack F, Baxter I, Harrison B, Grigor J, et al. Comparison of three approaches to assess the flavour characteristics of scotch whisky spirit. Applied Sciences. 2021;11(4):1410. https://doi.org/10.3390/app11041410
5. Matthews AC. Beverage flavourings and their applications. In: Ashurst PR, editors. Food Flavourings. Boston: Springer; 1991, pp. 158–184. https://doi.org/10.1007/978-1-4613-0499-9_6
6. der Heijden KV. International food safety handbook: Science, international regulation, and control. NY: Routledge; 2019. 832 p. https://doi.org/10.1201/9780203750346
7. Kamiloglu S. Authenticity and traceability in beverages. Food Chemistry. 2019;277:12–24. https://doi.org/10.1016/ j.foodchem.2018.10.091
8. Oberenko AV, Seleznev VM. The flavors in the composition of cognacs, withdrawn from illegal circulation on the territory of Krasnoyarsk region. The Bulletin of KrasGAU. 2019;143(2):144–149. (In Russ.) https://elibrary.ru/VWNIEO
9. Valand R, Tanna S, Lawson G, Bengtström L. A review of fourier transform infrared (FTIR) spectroscopy used in food adulteration and authenticity investigations. Food Additives & Contaminants: Part A. 2020;37(1):19–38. https://doi.org/10.1080/ 19440049.2019.1675909
10. Guillen MD, Manzanos MJ, Zabala L. Study of a commercial liquid smoke flavouring by means of gas chromato- graphy/Mass spectrometry and fourier transform infrared spectroscopy. Journal of Agricultural and Food Chemistry. 1995; 43(2):463–468. https://doi.org/10.1021/jf00050a039
11. Peng J, Yang Y, Zhou Y, Hocart CH, Zhao H, et al. Headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry with selected ion monitoring for the determination of four food flavouring compounds and its application in identifying artificially scented rice. Food Chemistry. 2020;313:126136. https://doi.org/10.1016/j.foodchem. 2019.126136
12. Rusli NS, Embong Z, Muhammad N, Wahab AA, Jafery KM, et al. Attenuated total reflectance – Fourier transform infrared (ATR-FTIR) spectroscopy analysis for O-H, C-H and C-O functional group in major carrier solvents of raw e-cigarette liquids (PG and VG). AIP Conference Proceedings. 2022;2454(1):030013. https://doi.org/10.1063/5.0078540
13. Gemma G, Cucinotta L, Rotondo A, Donato P, Mondello L, et al. Expanding the knowledge related to flavors and fragrances by means of three-dimensional preparative gas chromatography and molecular spectroscopy. Separations. 2022;9(8): 202. https://doi.org/10.3390/separations9080202
14. Hong JM, Kim TW, Lee SJ. Sensory and volatile profiles of Korean commercially distilled soju using descriptive analysis and HS-SPME-GC-MS. Foods. 2020;9(9):1330. https://doi.org/10.3390/foods9091330
15. Kang H-R, Hwang H-J, Lee JE, Kim HR. Quantitative analysis of volatile flavor components in Korean alcoholic beverage and Japanese sake using SPME-GC-MS. Food science and biotechnology. 2016;25:979–985. https://doi.org/10.1007/ s10068-016-0159-7
16. Ma L, Gao W, Chen F, Meng Q. HS-SPME and SDE combined with GC–MS and GC–O for characterization of flavor compounds in Zhizhonghe Wujiapi medicinal liquor. Food Research International. 2020;137:109590. https://doi.org/ 10.1016/j.foodres.2020.109590
17. Muñoz-Redondo JM, Valcárcel-Muñoz MJ, Solana RR, Puertas B, Cantos-Villar E, et al. Development of a methodology based on headspace solid-phase microextraction coupled to gas chromatography-mass spectrometry for the analysis of esters in brandies. Journal of Food Composition and Analysis. 2022;108:104458. https://doi.org/10.1016/j.jfca.2022.104458
18. Tarhan İ, Bakır MR, Kalkan O, Yöntem M, Kara H. Rapid determination of adulteration of clove essential oil with benzyl alcohol and ethyl acetate: Towards quality control analysis by FTIR with chemometrics. Vibrational Spectroscopy. 2022;118:103339. https://doi.org/10.1016/j.vibspec.2022.103339
19. Xia Y, Liu Y, Wang J, Shuang Q. Assessment of key aroma compounds in fresh jujube brandy by GC-O-MS and odor activity value. Journal of Food Processing and Preservation. 2020;44(7):e14494. https://doi.org/10.1111/jfpp.14494
20. Gao Y, Li X-Y, Wang Q-L, Li Z-H, Chi S-X, et al. Quantification of crucial odorants dominating the characteristic flavor of beer by FTIR combined with machine learning approaches. SSRN. 2023. http://dx.doi.org/10.2139/ssrn.4463417
21. Deconinck E, Bothy JL, Barhdadi S, Courselle P. Discriminating nicotine and non-nicotine containing e-liquids using infrared spectroscopy. Journal of Pharmaceutical and Biomedical Analysis. 2016;120:333–341. https://doi.org/10.1016/ j.jpba.2015.12.054
22. Wang F, Shao C, Chen Q, Meng T, Li C. Application on sensory prediction of Chinese Moutai-flavour liquor based on ATR-FTIR. E3S Web of Conferences. 2019;79:03001. https://doi.org/10.1051/e3sconf/20197903001
23. Akhtar Z, Barhdadi S, de Braekeleer K, Delporte C, Adams E, et al. Spectroscopy and chemometrics for conformity analysis of e-liquids: Illegal additive detection and nicotine characterization. Chemosensors. 2024;12(1):9. https://doi.org/10.3390/ chemosensors12010009
24. Belchior V, Botelho BG, Oliveira LS, Franca AS. Attenuated total reflectance fourier transform spectroscopy (ATR-FTIR) and chemometrics for discrimination of espresso coffees with different sensory characteristics. Food Chemistry. 2019;273:178–185. https://doi.org/10.1016/j.foodchem.2017.12.026
25. Mondragón-Cortezl PM, Herrera-López EJ, Arriola-Guevara E, Guatemala-Morales GM. Application of fourier transform infrared spectroscopy (FTIR) in combination with attenuated total reflection (ATR) for rapid analysis of the tequila production process. Revista Mexicana de Ingeniería Química. 2022;21(3):1–11. https://doi.org/10.24275/rmiq/Alim2806
26. Rebiai A, Hemmami H, Zeghoud S, Seghir BB, Kouadri I, et al. Current application of chemometrics analysis in authentication of natural products: A review. Combinatorial Chemistry & High Throughput Screening. 2022;25(6):945–972. https://doi.org/10.2174/1386207324666210309102239
27. Randriamihamison N, Vialaneix N, Neuvial P. Applicability and interpretability of Ward’s hierarchical agglomerative clustering with or without contiguity constraints. Journal of Classification. 2021;38:363–389. https://doi.org/10.1007/s00357- 020-09377-y
28. Li Y, Li Q, Zhang B, Shen C, Xu Y, et al. Identification, quantitation and sensorial contribution of lactones in brandies between China and France. Food Chemistry. 2021;357:129761. https://doi.org/10.1016/j.foodchem.2021.129761
29. Thibaud F, Courregelongue M, Darriet P. Contribution of volatile odorous terpenoid compounds to aged cognac spirits aroma in a context of multicomponent odor mixtures. Journal of Agricultural and Food Chemistry. 2020;68(47):13310–13318. https://doi.org/10.1021/acs.jafc.9b06656
30. Nie X, Liu K, Zhang Y, Wang Z, Meng C, et al. Effects of oak chips on quality and flavor of persimmon brandy: A comprehensive analysis of volatile and non-volatile compounds. LWT. 2023;183:114915. https://doi.org/10.1016/j.lwt.2023.114915
31. Crowell EA, Guymon JF. Studies of caprylic, capric, lauric, and other free fatty acids in brandies by gas chromatography. American Journal of Enology and Viticulture. 1969;20(3):155–163. https://doi.org/10.5344/ajev.1969.20.3.155
32. Eliseev MN, Gribkova IN, Kosareva OA, Alexeyeva OM. Effect of organic compounds on cognac sensory profile. Foods and Raw Materials. 2021;9(2):244–253. http://doi.org/10.21603/2308-4057-2021-2-244-253
33. Ma Y, Li Y, Zhang B, Shen C, Yu L, et al. Chemosensory characteristics of brandies from Chinese core production area and first insights into their differences from cognac. Foods. 2023;13(1):27. https://doi.org/10.3390/foods13010027
34. Li S, Yang H, Tian H, Zou J, Li J. Correlation analysis of the age of brandy and volatiles in brandy by gas chromatography-mass spectrometry and gas chromatography-ion mobility spectrometry. Microchemical Journal. 2020;157:104948. https://doi.org/10.1016/j.microc.2020.104948
35. Kelly TJ, O’Connor C, Kilcawley KN. Sources of volatile aromatic congeners in whiskey. Beverages. 2023;9(3):64. https://doi.org/10.3390/beverages9030064
36. Warren-Vega WM, Rocio FA, González-Gutiérrez LV, Carrasco-Marin F, Zarate-Guzmán AI, et al. Chemical characterization of tequila maturation process and their connection with the physicochemical properties of the cask. Journal of Food Composition and Analysis. 2021;98:103804. https://doi.org/10.1016/j.jfca.2021.103804
37. Wang L, Chen S, Xu Y. Distilled beverage aging: A review on aroma characteristics, maturation mechanisms, and artificial aging techniques. Comprehensive Reviews in Food Science and Food Safety. 2023;22(1):502–534. https://doi.org/ 10.1111/1541-4337.13080