Volatilomics Profiling of Counterfeit Perfume by Gas Chromatography Hyphenated to Mass Spectrometry and Fourier-Transformed Infrared Spectroscopy
Siti Nurul Hidayah(1*), Artania Adnin Tri Suma(2), Endang Lukitaningsih(3)
(1) Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(2) Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(3) Department of Pharmaceutical Chemistry, Faculty of Pharmacy, Universitas Gadjah Mada, Sekip Utara, Yogyakarta 55281, Indonesia
(*) Corresponding Author
Abstract
To prevent deleterious effects on consumers and potential health damage caused by counterfeit perfumes, this study aims to distinguish the original perfume from its suspected counterfeit products. Fingerprint and volatilomics profiling was performed using attenuated total reflection-Fourier infrared spectroscopy (ATR-FTIR) and gas chromatography hyphenated to mass spectrometry (GC-MS). Headspace (HS)-GC-MS was optimized to analyze perfume samples containing water. In the presence of water, our optimized HS-GC-MS method shows linalool's consistent signal intensity, providing an alternative analytical method for water-based perfume formulation. The GC-MS chemical characterization revealed 45 compounds detected in the original sample but only four compounds were detected in the counterfeit products: linalool, citronellol, methyl jasmonate, acetic acid, and propanol. This suggests a clear difference in the formulation of counterfeit products. Counterfeit products also cheat by using a lower amount of ingredients. Relative quantification shows that linalool in counterfeit products was as low as only 5.1% of the amount in the original product. In addition, cheaper and hazardous materials like methanol and 6,7-dihydrogeraniol were detected in counterfeit products. The combination of ATR-FTIR, GC-MS, and HS-GC-MS demonstrated fast authentication of counterfeit perfumes for routine quality control purposes and the possibility of water-based perfume analysis.
Keywords
Full Text:
Full Text PDFReferences
[1] Rodrigues, A.E., Nogueira, I., and Faria, R.P.V., 2021, Perfume and flavor engineering: A chemical engineering perspective, Molecules, 26 (11), 3095.
[2] Kumar, M., Devi, A., Sharma, M., Kaur, P., and Mandal, U.K., 2021, Review on perfume and present status of its associated allergens, J. Cosmet. Dermatol., 20 (2), 391–399.
[3] Sowndhararajan, K., and Kim, S., 2016, Influence of fragrances on human psychophysiological activity: With special reference to human electroencephalographic response, Sci. Pharm., 84 (4), 724–751.
[4] Abedi, G., Talebpour, Z., and Jamechenarboo, F., 2018, The survey of analytical methods for sample preparation and analysis of fragrances in cosmetics and personal care products, TrAC, Trends Anal. Chem., 102, 41–59.
[5] Burger, P., Plainfossé, H., Brochet, X., Chemat, F., and Fernandez, X., 2019, Extraction of natural fragrance ingredients: History overview and future trends, Chem. Biodiversity, 16 (10), e1900424.
[6] Brown, A., Mettetal, A., and Hettiarachchi, D., 2022, “Sandalwood—Perfumery” in Materials Horizons: from Nature to Nanomaterials, Eds. Arunkumar, A.N., Joshi, G., Warrier, R.R., and Karaba, N.N., Springer Nature, Singapore, 449–461.
[7] Lecourt, M., and Antoniotti, S., 2020, Chemistry, sustainability and naturality of perfumery biotech ingredients, ChemSusChem, 13 (21), 5600–5610.
[8] Chaudhry, P., and Zimmerman, A., 2013, “The Global Growth of Counterfeit Trade” in Protecting Your Intellectual Property Rights: Understanding the Role of Management, Governments, Consumers and Pirates, Springer, New York, US, 7–31.
[9] Pierson, M., Fernandez, X., and Antoniotti, S., 2021, Type and magnitude of non-compliance and adulteration in neroli, mandarin and bergamot essential oils purchased on-line: potential consumer vulnerability, Sci. Rep., 11 (1), 11096.
[10] Lubes, G., and Goodarzi, M., 2017, Analysis of volatile compounds by advanced analytical techniques and multivariate chemometrics, Chem. Rev., 117 (9), 6399–6422.
[11] Kempińska-Kupczyk, D., and Kot-Wasik, A., 2019, The potential of LC–MS technique in direct analysis of perfume content, Monatsh. Chem., 150 (9), 1617–1623.
[12] Bounaas, K., Bouzidi, N., Daghbouche, Y., Garrigues, S., de la Guardia, M., and El Hattab, M., 2018, Essential oil counterfeit identification through middle infrared spectroscopy, Microchem. J., 139, 347–356.
[13] Cebi, N., 2021, Quantification of the geranium essential oil, palmarosa essential oil and phenylethyl alcohol in Rosa damascena essential oil using ATR-FTIR spectroscopy combined with chemometrics, Foods, 10 (8), 1848.
[14] Lebanov, L., Tedone, L., Ghiasvand, A., and Paull, B., 2020, Characterisation of complex perfume and essential oil blends using multivariate curve resolution-alternating least squares algorithms on average mass spectrum from GC-MS, Talanta, 219, 121208.
[15] Xiao, Z., Luo, J., Niu, Y., and Wu, M., 2018, Characterization of key aroma compounds from different rose essential oils using gas chromatography-mass spectrometry, gas chromatography–olfactometry and partial least squares regression, Nat. Prod. Res., 32 (13), 1567–1572.
[16] Feng, Y., Cheng, X., Lu, Y., Wang, H., Chen, D., Luo, C., Liu, H., Gao, S., Lei, T., Huang, C., and Yu, X., 2022, Gas chromatography-mass spectrometry analysis of floral fragrance-related compounds in scented rose (Rosa hybrida) varieties and a subsequent evaluation on the basis of the analytical hierarchy process, Plant Physiol. Biochem., 185, 368–377.
[17] Gasparini, G., Semaoui, S., Augugliaro, J., Boschung, A., Berthier, D., Seyfried, M., and Begnaud, F., 2020, Quantification of residual perfume by Py-GC-MS in fragrance encapsulate polymeric materials intended for biodegradation tests, Molecules, 25 (3), 718.
[18] Cebi, N., Arici, M., and Sagdic, O., 2021, The famous Turkish rose essential oil: Characterization and authenticity monitoring by FTIR, Raman and GC–MS techniques combined with chemometrics, Food Chem., 354, 129495.
[19] Wei, L., Wei, S., Hu, D., Feng, L., Liu, Y., Liu, H., and Liao, W., 2022, Comprehensive flavor analysis of volatile components during the vase period of cut lily (Lilium spp. ‘Manissa’) flowers by HS-SPME/GC–MS combined with E-nose technology, Front. Plant Sci., 13, 822956.
[20] Popova, V., Ivanova, T., Stoyanova, A., Nikolova, V., Hristeva, T., and Zheljazkov, V.D., 2020, GC-MS Composition and olfactory profile of concretes from the flowers of four Nicotiana species, Molecules, 25 (11), 2617.
[21] Rangarajan, R., and Ghosh, P., 2011, Role of water contamination within the GC column of a GasBench II peripheral on the reproducibility of 18O/16O ratios in water samples, Isot. Environ. Health Stud., 47 (4), 498–511.
[22] Mazzucotelli, M., Minteguiaga, M.A., Sgorbini, B., Sidisky, L., Marengo, A., Rubiolo, P., Bicchi, C., and Cagliero, C., 2020, Ionic liquids as water-compatible GC stationary phases for the analysis of fragrances and essential oils: Quantitative GC–MS analysis of officially-regulated allergens in perfumes, J. Chromatogr. A, 1610, 460567.
[23] Riboni, N., Fornari, F., Bianchi, F., and Careri, M., 2021, A simple and efficient solid-phase microextraction – gas chromatography – mass spectrometry method for the determination of fragrance materials at ultra-trace levels in water samples using multi-walled carbon nanotubes as innovative coating, Talanta, 224, 121891.
[24] Satpathy, G., 2013, Analysis of Volatile Organic Compounds in Water Using Static Headspace GC/MS, Application Note, Bruker Daltonik GmbH, Bremen, Germany.
[25] Huang, B., Yan, D., Fang, W., Wang, X., Liu, J., Zhang, D., Wang, Q., Ouyang, C., Han, Q., Jin, X., and Cao, A., 2020, Comparison of headspace solid-phase microextraction and solvent extraction method for the simultaneous analysis of various soil fumigants in soil or water by gas chromatography–mass spectrometry, J. Sep. Sci., 43 (8), 1499–1513.
[26] González-Hernández, P., Pacheco-Fernández, I., Bernardo, F., Homem, V., Pasán, J., Ayala, J.H., Ratola, N., and Pino, V., 2021, Headspace solid-phase microextraction based on the metal-organic framework CIM-80(Al) coating to determine volatile methylsiloxanes and musk fragrances in water samples using gas chromatography and mass spectrometry, Talanta, 232, 122440.
[27] Lehner, A.F., and Buchweitz, J.P., 2022, Benefits and malefits of solvent vent mode in combination with tandem mass spectrometry for static headspace analysis of organic solvents by gas chromatography, Chromatographia, 85 (4), 315–331.
[28] Sithersingh, M.J., and Snow, N.H., 2021, “Headspace gas chromatography” in Gas Chromatography, Eds. Poole, C.F., Elsevier, Amsterdam, Netherland, 251–265.
[29] Rossi, L., Foschi, M., Biancolillo, A., Maggi, M.A., and D’Archivio, A.A., 2023, Optimization of HS-SPME-GC/MS analysis of wine volatiles supported by chemometrics for the aroma profiling of Trebbiano d’Abruzzo and Pecorino white wines produced in Abruzzo (Italy), Molecules, 28 (4), 1534.
[30] Chan, M., Sy, H., Finley, J., Robertson, J., and Brown, P.N., 2021, Determination of ethanol content in kombucha using headspace gas chromatography with mass spectrometry detection: Single-laboratory validation, J. AOAC Int., 104 (1), 122–128.
[31] Taylor, L., Remeškevičius, V., Saskoy, L., Brodie, T., Mahmud, J., Moir, H., Brouner, J., Howe, C., Thatti, B., O’Connell, S., Trotter, G., and Rooney, B., 2020, Determination of ethanol in micro-volumes of blood by headspace gas chromatography: Statistical comparison between capillary and venous sampling sites, Med., Sci. Law, 61 (2), 86–96.
[32] Aspromonte, J., Giacoppo, G., Wolfs, K., and Adams, E., 2020, Headspace gas chromatography for the determination of volatile methylsiloxanes in personal care products, Anal. Bioanal. Chem., 412 (11), 2537–2544.
[33] Chen, J., Yi, Z., Yin, J., Dong, S., Wang, L., and Li, Y., 2023, Determination of fragrance allergens in paper personal care products by headspace (HS) solid-phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS) with response surface methodology (RSM) optimization, Anal. Lett., 56 (12), 1868–1883.
[34] Hartonen, K., Helin, A., Parshintsev, J., and Riekkola, M.L., 2019, Problems caused by moisture in gas chromatographic analysis of headspace SPME samples of short-chain amines, Chromatographia, 82 (1), 307–316.
[35] Remy, P.A., Pérès, C., Dugay, J., Corbi, E., David, N., and Vial, J., 2021, How high-resolution mass spectrometry can help for the accurate quantification of difficult fragrance allergens, Flavour Fragrance J., 36 (2), 243–255.
[36] Batou, A., 2019, A sensitivity-based one-parameter-at-a-time model updating method, Mech. Syst. Signal Process., 122, 247–255.
[37] Bell, J., Nel, P., and Stuart, B., 2019, Non-invasive identification of polymers in cultural heritage collections: Evaluation, optimisation and application of portable FTIR (ATR and external reflectance) spectroscopy to three-dimensional polymer-based objects, Heritage Sci., 7 (1), 95.
[38] Tarhan, İ., Çelikten, Ş., Kestek, H.M., Çelik, B., Öner, M., Kenar, A., and Kara, H., 2023, Development of a new and rapid FTIR method using chemometric modeling techniques for the determination of lavandin adulteration in lavender essential oil, Vib. Spectrosc., 127, 103559.
[39] Mohammed, W.B., Tarabzouni, S., and Bohlega, S., 2022, Methanol-induced parkinsonism and cerebral vasculopathy due to perfume inhalation, BMJ Neurol. Open, 4 (1), e000221.
[40] Chan, A.P.L., and Chan, T.Y.K., 2018, Methanol as an unlisted ingredient in supposedly alcohol-based hand rub can pose serious health risk, Int. J. Environ. Res. Public Health, 15 (7), 1440.
[41] Scientific Committee on Cosmetic Products and Non-food Products Intended for Consumers, 2003, The SCCNFP’S Notes of Guidance for Testing of Cosmetic Ingredients and Their Safety Evaluation, 5th revision, Directorate-General for Health and Consumer Protection of the European Commission, Brussel, Belgium.
[42] Rádis-Baptista, G., 2023, Do synthetic fragrances in personal care and household products impact indoor air quality and pose health risks?, J. Xenobiot., 13 (1), 121–131.
[43] Hwang, J.B., Lee, S., Yeum, J., Kim, M.K., Choi, J.C., Park, S.J., and Kim, J., 2019, HS-GC/MS method development and exposure assessment of volatile organic compounds from food packaging into food simulants, Food Addit. Contam.: Part A, 36 (10), 1574–1583.
DOI: https://doi.org/10.22146/ijc.96313
Article Metrics
Abstract views : 587 | views : 411Copyright (c) 2024 Indonesian Journal of Chemistry
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.
View The Statistics of Indones. J. Chem.