Detection of Adulterated Oregano Samples Using Untargeted Headspace–Gas Chromatography–Ion Mobility Spectrometry Analysis
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents
2.2. Oregano Samples
2.3. Instrumentation and Software
2.4. HS-GC-IMS Method
2.5. Chemometric Data Processing
3. Results and Discussion
3.1. Optimization of the HS-GC-IMS Method
3.2. Identification of VOCs
3.3. Characterization of HS-GC-IMS Method
3.4. Quantification of Identified VOCs
3.5. Chemometric Models
3.5.1. OPLS-DA for the Detection of Samples Adulterated with Olive Leaves
3.5.2. PLS for Quantification of the Olive Leaves Content in Oregano Samples
3.6. Analysis of Commercial Oregano Samples and Comparison with Other Reported Methodologies
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Kintzios, S.E. Profile of the Multifaceted Prince of the Herbs. In Oregano: The Genera Origanum and Lippia; Kintzios, S.E., Ed.; CRC Press: London, UK, 2002; pp. 3–10. [Google Scholar]
- Black, C.; Haughey, S.A.; Chevallier, O.P.; Galvin-King, P.; Elliott, C.T. A Comprehensive Strategy to Detect the Fraudulent Adulteration of Herbs: The Oregano Approach. Food Chem. 2016, 210, 551–557. [Google Scholar] [CrossRef]
- ISO-7925; Dried Oregano (Origanum vulgare L.). ISO: Geneva, Switzerland, 2015.
- Council of Europe. Oregano Monograph 01/2005:1880. In European Pharmacopoeia; Council of Europe: Strasbourg, France, 2005; pp. 2155–2156. [Google Scholar]
- Massaro, A.; Negro, A.; Bragolusi, M.; Miano, B.; Tata, A.; Suman, M.; Piro, R. Oregano Authentication by Mid-Level Data Fusion of Chemical Fingerprint Signatures Acquired by Ambient Mass Spectrometry. Food Control 2021, 126, 108058. [Google Scholar] [CrossRef]
- Everstine, K.; Spink, J.; Kennedy, S. Economically Motivated Adulteration (EMA) of Food: Common Characteristics of EMA Incidents. J. Food Prot. 2013, 76, 723–735. [Google Scholar] [CrossRef] [PubMed]
- European Spice Association the Spices Post. Available online: https://www.esa-spices.org/index-esa.html/publications-esa/the-spices-post (accessed on 30 January 2024).
- Marieschi, M.; Torelli, A.; Poli, F.; Sacchetti, G.; Bruni, R. RAPD-Based Method for the Quality Control of Mediterranean Oregano and Its Contribution to Pharmacognostic Techniques. J. Agric. Food Chem. 2009, 57, 1835–1840. [Google Scholar] [CrossRef]
- ASTA: The Voice of the U.S. Spice Industry in the Global Market. Available online: https://www.astaspice.org/ (accessed on 24 January 2023).
- European Spice Association. Available online: https://www.esa-spices.org/ (accessed on 24 January 2023).
- Maquet, A.; Lievens, A.; Paracchini, V.; Kaklamanos, G.; de la Calle, B.; Garlant, L.; Papoci, S.; Pietretti, D.; Zdiniakova, T.; Breidbach, A.; et al. Results of an EU Wide Coordinated Control Plan to Establish the Prevalence of Fraudulent Practices in the Marketing of Herbs and Spices-Publications Office of the EU; Publications Office of the European Union: Luxembourg, 2021. [Google Scholar]
- Wielogorska, E.; Chevallier, O.; Black, C.; Galvin-King, P.; Delêtre, M.; Kelleher, C.T.; Haughey, S.A.; Elliott, C.T. Development of a Comprehensive Analytical Platform for the Detection and Quantitation of Food Fraud Using a Biomarker Approach. The Oregano Adulteration Case Study. Food Chem. 2018, 239, 32–39. [Google Scholar] [CrossRef] [PubMed]
- Bononi, M.; Tateo, F. LC-ESI-MS/MS Identification of Oleuropein as Marker of Olea europaea L. Leaves Used as a Bulking Agent in Ground Oregano and Sage. Ital. J. Food Sci. 2011, 23, 245–251. [Google Scholar]
- Ivanović, S.; Mandrone, M.; Simić, K.; Ristić, M.; Todosijević, M.; Mandić, B.; Gođevac, D. GC-MS-Based Metabolomics for the Detection of Adulteration in Oregano Samples. J. Serbian Chem. Soc. 2021, 86, 1195–1203. [Google Scholar] [CrossRef]
- Drabova, L.; Alvarez-Rivera, G.; Suchanova, M.; Schusterova, D.; Pulkrabova, J.; Tomaniova, M.; Kocourek, V.; Chevallier, O.; Elliott, C.; Hajslova, J. Food Fraud in Oregano: Pesticide Residues as Adulteration Markers. Food Chem. 2019, 276, 726–734. [Google Scholar] [CrossRef] [PubMed]
- Creydt, M.; Flügge, F.; Dammann, R.; Schütze, B.; Günther, U.L.; Fischer, M. Food Fingerprinting: LC-ESI-IM-QTOF-Based Identification of Blumeatin as a New Marker Metabolite for the Detection of Origanum Majorana Admixtures to O. Onites/Vulgare. Metabolites 2023, 13, 673. [Google Scholar] [CrossRef]
- Damiani, T.; Dreolin, N.; Stead, S.; Dall’Asta, C. Critical Evaluation of Ambient Mass Spectrometry Coupled with Chemometrics for the Early Detection of Adulteration Scenarios in Origanum vulgare L. Talanta 2021, 227, 122116. [Google Scholar] [CrossRef]
- Zacometti, C.; Massaro, A.; di Gioia, T.; Lefevre, S.; Frégière-Salomon, A.; Lafeuille, J.L.; Fiordaliso Candalino, I.; Suman, M.; Piro, R.; Tata, A. Thermal Desorption Direct Analysis in Real-Time High-Resolution Mass Spectrometry and Machine Learning Allow the Rapid Authentication of Ground Black Pepper and Dried Oregano: A Proof-of-Concept Study. J. Mass Spectrom. 2023, 58, e4953. [Google Scholar] [CrossRef]
- Mandrone, M.; Marincich, L.; Chiocchio, I.; Petroli, A.; Gođevac, D.; Maresca, I.; Poli, F. NMR-Based Metabolomics for Frauds Detection and Quality Control of Oregano Samples. Food Control 2021, 127, 108141. [Google Scholar] [CrossRef]
- Flügge, F.; Kerkow, T.; Kowalski, P.; Bornhöft, J.; Seemann, E.; Creydt, M.; Schütze, B.; Günther, U.L. Qualitative and Quantitative Food Authentication of Oregano Using NGS and NMR with Chemometrics. Food Control 2023, 145, 109497. [Google Scholar] [CrossRef]
- Fiorani, L.; Lai, A.; Puiu, A.; Artuso, F.; Ciceroni, C.; Giardina, I.; Pollastrone, F. Laser Sensing and Chemometric Analysis for Rapid Detection of Oregano Fraud. Sensors 2023, 23, 6800. [Google Scholar] [CrossRef] [PubMed]
- Marieschi, M.; Torelli, A.; Bianchi, A.; Bruni, R. Detecting Satureja montana L. and Origanum majorana L. by Means of SCAR–PCR in Commercial Samples of Mediterranean Oregano. Food Control 2011, 22, 542–548. [Google Scholar] [CrossRef]
- Marieschi, M.; Torelli, A.; Bianchi, A.; Bruni, R. Development of a SCAR Marker for the Identification of Olea europaea L.: A Newly Detected Adulterant in Commercial Mediterranean Oregano. Food Chem. 2011, 126, 705–709. [Google Scholar] [CrossRef]
- Marieschi, M.; Torelli, A.; Poli, F.; Bianchi, A.; Bruni, R. Quality Control of Commercial Mediterranean Oregano: Development of SCAR Markers for the Detection of the Adulterants Cistus incanus L., Rubus caesius L. and Rhus coriaria L. Food Control 2010, 21, 998–1003. [Google Scholar] [CrossRef]
- Raclariu-Manolică, A.C.; Anmarkrud, J.A.; Kierczak, M.; Rafati, N.; Thorbek, B.L.G.; Schrøder-Nielsen, A.; de Boer, H.J. DNA Metabarcoding for Quality Control of Basil, Oregano, and Paprika. Front. Plant Sci. 2021, 12, 665618. [Google Scholar] [CrossRef] [PubMed]
- McGrath, T.F.; Haughey, S.A.; Islam, M.; Elliott, C.T. The Potential of Handheld near Infrared Spectroscopy to Detect Food Adulteration: Results of a Global, Multi-Instrument Inter-Laboratory Study. Food Chem. 2021, 353, 128718. [Google Scholar] [CrossRef]
- Rodionova, O.Y.; Pomerantsev, A.L. Chemometric Tools for Food Fraud Detection: The Role of Target Class in Non-Targeted Analysis. Food Chem. 2020, 317, 126448. [Google Scholar] [CrossRef]
- Van De Steene, J.; Ruyssinck, J.; Fernandez-Pierna, J.A.; Vandermeersch, L.; Maes, A.; Van Langenhove, H.; Walgraeve, C.; Demeestere, K.; De Meulenaer, B.; Jacxsens, L.; et al. Authenticity Analysis of Oregano: Development, Validation and Fitness for Use of Several Food Fingerprinting Techniques. Food Res. Int. 2022, 162, 111962. [Google Scholar] [CrossRef]
- McVey, C.; McGrath, T.F.; Haughey, S.A.; Elliott, C.T. A Rapid Food Chain Approach for Authenticity Screening: The Development, Validation and Transferability of a Chemometric Model Using Two Handheld near Infrared Spectroscopy (NIRS) Devices. Talanta 2021, 222, 121533. [Google Scholar] [CrossRef]
- Arroyo-Manzanares, N.; Martín-Gómez, A.; Jurado-Campos, N.; Garrido-Delgado, R.; Arce, C.; Arce, L. Target vs Spectral Fingerprint Data Analysis of Iberian Ham Samples for Avoiding Labelling Fraud Using Headspace–Gas Chromatography–Ion Mobility Spectrometry. Food Chem. 2018, 246, 65–73. [Google Scholar] [CrossRef]
- Arroyo-Manzanares, N.; García-Nicolás, M.; Castell, A.; Campillo, N.; Viñas, P.; López-García, I.; Hernández-Córdoba, M. Untargeted Headspace Gas Chromatography–Ion Mobility Spectrometry Analysis for Detection of Adulterated Honey. Talanta 2019, 205, 120123. [Google Scholar] [CrossRef] [PubMed]
- Arce, L. Ion Mobility Spectrometry. Encycl. Anal. Chem. 2010. [Google Scholar] [CrossRef]
- Vautz, W.; Franzke, J.; Zampolli, S.; Elmi, I.; Liedtke, S. On the Potential of Ion Mobility Spectrometry Coupled to GC Pre-Separation–A Tutorial. Anal. Chim. Acta 2018, 1024, 52–64. [Google Scholar] [CrossRef] [PubMed]
- Milos, M.; Mastelic, J.; Jerkovic, I. Chemical Composition and Antioxidant Effect of Glycosidically Bound Volatile Compounds from Oregano (Origanum vulgare L. Ssp. Hirtum). Food Chem. 2000, 71, 79–83. [Google Scholar] [CrossRef]
- Talhaoui, N.; Taamalli, A.; Gómez-Caravaca, A.M.; Fernández-Gutiérrez, A.; Segura-Carretero, A. Phenolic Compounds in Olive Leaves: Analytical Determination, Biotic and Abiotic Influence, and Health Benefits. Food Res. Int. 2015, 77, 92–108. [Google Scholar] [CrossRef]
- Węglarz, Z.; Kosakowska, O.; Przybył, J.L.; Pióro-Jabrucka, E.; Baczek, K. The Quality of Greek Oregano (O. vulgare L. Subsp. Hirtum (Link) Ietswaart) and Common Oregano (O. vulgare L. Subsp. Vulgare) Cultivated in the Temperate Climate of Central Europe. Foods 2020, 9, 1671. [Google Scholar] [CrossRef]
- Malheiro, R.; Casal, S.; Cunha, S.C.; Baptista, P.; Pereira, J.A. Identification of Leaf Volatiles from Olive (Olea Europaea) and Their Possible Role in the Ovipositional Preferences of Olive Fly, Bactrocera Oleae (Rossi) (Diptera: Tephritidae). Phytochemistry 2016, 121, 11–19. [Google Scholar] [CrossRef]
- Contreras, M.d.M.; Arroyo-Manzanares, N.; Arce, C.; Arce, L. HS-GC-IMS and Chemometric Data Treatment for Food Authenticity Assessment: Olive Oil Mapping and Classification through Two Different Devices as an Example. Food Control 2019, 98, 82–93. [Google Scholar] [CrossRef]
- Bajoub, A.; Pacchiarotta, T.; Hurtado-Fernández, E.; Olmo-García, L.; García-Villalba, R.; Fernández-Gutiérrez, A.; Mayboroda, O.A.; Carrasco-Pancorbo, A. Comparing Two Metabolic Profiling Approaches (Liquid Chromatography and Gas Chromatography Coupled to Mass Spectrometry) for Extra-Virgin Olive Oil Phenolic Compounds Analysis: A Botanical Classification Perspective. J. Chromatogr. A 2016, 1428, 267–279. [Google Scholar] [CrossRef] [PubMed]
- Wang, Q.; Gao, P.; Wang, X.; Duan, Y. The Early Diagnosis and Monitoring of Squamous Cell Carcinoma via Saliva Metabolomics. Sci. Rep. 2014, 4, 1–9. [Google Scholar] [CrossRef]
- Sadergaski, L.R.; Hager, T.J.; Andrews, H.B. Design of Experiments, Chemometrics, and Raman Spectroscopy for the Quantification of Hydroxylammonium, Nitrate, and Nitric Acid. ACS Omega 2022, 7, 7287–7296. [Google Scholar] [CrossRef]
- 1.1: Solubilidad-LibreTexts Español. Available online: https://espanol.libretexts.org/Quimica/Qu%C3%ADmica_Anal%C3%ADtica/An%C3%A1lisis_Cualitativo_de_Cationes_Comunes_en_Agua_(Malik)/1%3A_Principios_Qu%C3%ADmicos/1.1%3A_Solubilidad (accessed on 22 March 2023).
- García-Nicolás, M.; Pérez-Álvarez, M.C.; Abellán-Alfocea, F.; Arroyo-Manzanares, N.; Campillo, N.; del Val-Oliver, B.; Jiménez-Santos, E.; Zarauz-García, J.; Sáenz, L.; Viñas, P. Ion Mobility Spectrometry for the Metabolomic Study of Inflammatory Bowel Disease Using the Volatile Organic Compounds Profile in Human Serum and Urine. Chemosensors 2023, 11, 139. [Google Scholar] [CrossRef]
- Xi, B.; Gu, H.; Baniasadi, H.; Raftery, D. Statistical Analysis and Modeling of Mass Spectrometry-Based Metabolomics Data. Methods Mol. Biol. 2014, 1198, 333–353. [Google Scholar] [CrossRef]
- Triba, M.N.; Le Moyec, L.; Amathieu, R.; Goossens, C.; Bouchemal, N.; Nahon, P.; Rutledge, D.N.; Savarin, P. PLS/OPLS Models in Metabolomics: The Impact of Permutation of Dataset Rows on the K-Fold Cross-Validation Quality Parameters. Mol. Biosyst. 2014, 11, 13–19. [Google Scholar] [CrossRef] [PubMed]
- Parveen, I.; Gafner, S.; Techen, N.; Murch, S.J.; Khan, I.A. DNA Barcoding for the Identification of Botanicals in Herbal Medicine and Dietary Supplements: Strengths and Limitations. Planta Med. 2016, 82, 1225–1235. [Google Scholar] [CrossRef] [PubMed]
Compound | Percentages of Olive Leaves | |||||
---|---|---|---|---|---|---|
0% | 10% | 20% | 30% | 40% | 50% | |
2-butanone | 0.138 ± 0.005 | 0.11 ± 0.02 | NQ | NQ | NQ | NQ |
Ethyl acetate | NQ | NQ | NQ | NQ | NQ | NQ |
1-penten-3-one | NQ | NQ | NQ | NQ | NQ | NQ |
Valeraldehyde | 0.55 ± 0.02 | 0.9 ± 0.3 | 0.9 ± 0.3 | 0.7 ± 0.2 | 0.7 ± 0.2 | 0.6 ± 0.1 |
3-methyl-1-butanol | ND | NQ | NQ | NQ | NQ | NQ |
2-methyl-1-butanol | ND | ND | NQ | NQ | NQ | NQ |
Trans-2-pentenal | 0.503 ± 0.011 | 0.48 ± 0.03 | 0.43 ± 0.09 | 0.4 ± 0.1 | 0.4 ± 0.1 | 0.43 ± 0.08 |
1-pentanol | ND | NQ | NQ | NQ | NQ | NQ |
Hexanal | 1.19 ± 0.08 | 2.3 ± 0.7 | 1.8 ± 1.2 | 1.7 ± 1.2 | 1.6 ± 1.1 | 1.8 ± 0.9 |
Trans-2-hexen-1-ol | 8.9 ± 0.5 | 7.6 ± 0.6 | 6.4 ± 1.7 | 6 ± 2 | 5.1 ± 1.9 | 4.7 ± 1.2 |
1-hexanol | ND | ND | ND | ND | NQ | NQ |
Cis-2-hexen-1-ol | 0.529 ± 0.015 | 0.53 ± 0.05 | 0.51 ± 0.04 | 0.51 ± 0.07 | 0.55 ± 0.10 | 0.54 ± 0.10 |
Heptanal | 0.107 ± 0.005 | 0.114 ± 0.006 | NQ | NQ | NQ | 0.12 ± 0.03 |
Trans-2-heptenal | ND | NQ | NQ | NQ | NQ | NQ |
Benzaldehyde | 0.741 ± 0.016 | 0.825 ± 0.019 | 0.86 ± 0.09 | 0.87 ± 0.15 | 0.9 ± 0.2 | 0.9 ± 0.2 |
1-octen-3-one | 2.16 ± 0.06 | 2.3 ± 0.2 | 2.14 ± 0.18 | 2.1 ± 0.3 | 2.0 ± 0.3 | 2.0 ± 0.2 |
6-methyl-5-hepten-2-one | 0.99 ± 0.06 | 0.93 ± 0.12 | 0.97 ± 0.15 | 1.0 ± 0.3 | 1.0 ± 0.4 | 0.9 ± 0.3 |
2-pentylfuran | ND | ND | ND | ND | ND | ND |
Octanal | ND | ND | NQ | NQ | NQ | NQ |
Trans,trans-2,4-heptanodienal | NQ | NQ | NQ | NQ | NQ | NQ |
Limonene | >10 | >10 | >10 | >10 | >10 | >10 |
Trans-2-octenal | ND | ND | ND | ND | ND | ND |
Terpinolene | >10 | >10 | >10 | >10 | >10 | >10 |
Nonanal | ND | ND | ND | ND | ND | ND |
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content. |
© 2024 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
Share and Cite
Rocamora-Rivera, B.; Arroyo-Manzanares, N.; Viñas, P. Detection of Adulterated Oregano Samples Using Untargeted Headspace–Gas Chromatography–Ion Mobility Spectrometry Analysis. Foods 2024, 13, 516. https://doi.org/10.3390/foods13040516
Rocamora-Rivera B, Arroyo-Manzanares N, Viñas P. Detection of Adulterated Oregano Samples Using Untargeted Headspace–Gas Chromatography–Ion Mobility Spectrometry Analysis. Foods. 2024; 13(4):516. https://doi.org/10.3390/foods13040516
Chicago/Turabian StyleRocamora-Rivera, Blas, Natalia Arroyo-Manzanares, and Pilar Viñas. 2024. "Detection of Adulterated Oregano Samples Using Untargeted Headspace–Gas Chromatography–Ion Mobility Spectrometry Analysis" Foods 13, no. 4: 516. https://doi.org/10.3390/foods13040516