Synchronous Fluorescence Spectroscopy Method based on Chemometrics: Authentication of Extra Virgin Olive Oils Harvested in Mut (Mersin) Region and Refined Edible Oils
Year 2023,
Volume: 5 Issue: 2, 278 - 287, 31.12.2023
Fatma Nur Arslan
,
İsmail Varlı
Abstract
This study aims to gain insights into the prediction for the authentication of extra virgin olive oils (VOOs) from two different harvest terms (2019 and 2020 October) in Mut (Mersin) region and other refined edible oils from different brands. To pursue the research, an analytical approach based on synchronous fluorescence (SyF) spectroscopy combined with chemometrics including PCA and SIMCA was used. The SyF data were gathered in the emission region of 200–800 nm, and the emission/ excitation monochromators were synchronously used. The data of VOO and different types of edible oil samples were analyzed by the multivariate data analysis including PCA and SIMCA. It has been determined that the classification ability of oil types from different harvest terms is quite high by PCA score graphs; and the VOOs could be classified in a 100% different group from other oils by SIMCA. Consequently, the SyF spectroscopy combined with chemometrics is very advantageous methodology in terms of speed and cost, and it provides a great convenience by eliminating the laborious sample pre-treatments and chemical usage.
Supporting Institution
The study is financially supported by the Scientific Research Project Center of KMU with a project number 23–YL–20.
Thanks
The authors wish to acknowledge the Scientific Research Project Center of KMU due to their financial support. The study and a part of master thesis titled ''Development of Simple and Rapid Synchronous Fluorescence Spectroscopy Methods based on Chemometric Data Analysis Approach for the Classification and Adulteration of Olive Oils in Mut (Mersin) Region''.
References
- F.N. Arslan, ATR–FTIRspectroscopy combined with chemometrics for rapid classification of extra virgin olive oils and edible oils from different cultivars available on the Turkish markets, Eskişehir Technical University Journal of Science and Technology A- Applied Sciences and Engineering. 19 (2018), 926–947. doi:10.18038/aubtda.425374.
- I. Gouvinhas, J.M.M.M. De Almeida, T. Carvalho, N. Machado, A.I.R.N.A. Barros, Discrimination and characterisation of extra virgin olive oils from three cultivars in different maturation stages using Fourier transform infrared spectroscopy in tandem with chemometrics, Food Chemistry. 174 (2015), 226–232.
- G. Yildiz, T. Huseyin, Quantification of soybean oil adulteration in extra virgin olive oil using portable raman spectroscopy, Food Measurement and Charecterization. 11 (2017), 523–529. doi:10.1007/s11694-016-9419-8.
- İ. Varlı, Development of Simple and Rapid Synchronous Fluorescence Spectroscopy Methods based on Chemometric Data Analysis Approach for the Classification and Adulteration of Olive Oils in Mut (Mersin) Region, Master Thesis, Karamanoglu Mehmetbey University Institute of Science, Department of Chemistry, Karaman (2022).
- M.K. Demir, N. Bilgiçli, S. Türker, B. Demir, Farklı Stabilizasyon İşlemleri Uygulanmış Buğday Ruşeymlerinin Depolama Özellikleri, Necmettin Erbakan University Journal of Science and Engineering. 2 (2019), 67–75.
- M. Bevilacqua, R. Bucci, A.D. Magrì, A.L. Magrì, F. Marini, Tracing the origin of extra virgin olive oils by infrared spectroscopy and chemometrics: A case study, Analytica Chimica Acta. 717 (2012), 39–51. doi:10.1016/j.aca.2011.12.035.
- Lerma-Garcia, G. Ramis-ramos, J.J. Martinez-Tellez, Simo-Alfonso, Authentication of extra virgin olive oils by Fourier-transform infrared spectroscopy, Food Chemistry. 118 (2010), 78–83. doi:10.1016/j.foodchem.2009.04.092.
- G. Ozulku, R.M. Yildirim, O.S. Toker, S. Karasu, M.Z. Durak, Rapid detection of adulteration of cold pressed sesame oil adultered with hazelnut , canola , and sun fl ower oils using ATR-FTIR spectroscopy combined with chemometric, Food Control. 82 (2017), 212–216.
- P. De, A. Dominguez-vidal, J.M. Bosque-sendra, A. Ruiz-medina, L. Cuadros-rodríguez, M.J. Ayora-cañada, Olive oil assessment in edible oil blends by means of ATR-FTIR and chemometrics, Food Control. 23 (2012), 449–455. doi:10.1016/j.foodcont.2011.08.013.
- F. Mabood, R. Boqué, R. Folcarelli, O. Busto, A. Al-harrasi, J. Hussain, Thermal oxidation process accelerates degradation of the olive oil mixed with sunflower oil and enables its discrimination using synchronous fluorescence spectroscopy and chemometric analysis, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 143 (2015), 298–303. doi:10.1016/j.saa.2015.01.119.
- A. Dankowska, M. Małecka, W. Kowalewski, Application of synchronous fluorescence spectroscopy with multivariate data analysis for determination of butter adulteration, International Journal of Food Science and Technology. 49 (2014), 2628–2634. doi:10.1111/ijfs.12594.
- J. Cao, C. Li, R. Liu, X. Liu, Y. Fan, Z. Deng, Combined Application of Fluorescence Spectroscopy and Chemometrics Analysis in Oxidative Deterioration of Edible Oils, Food Analytical Methods. 10 (2017), 649–658. doi:10.1007/s12161-016-0587-2.
- K. Poulli, N. V Chantzos, G.A. Mousdis, C.A. Gorgiou, Synchronous Fluorescence Spectroscopy : Tool for Monitoring Thermally Stressed Edible Oils, Journal of Agricultural and Food Chemistry. 57 (2009), 8194–8201. doi:10.1021/jf902758d.
- F.N. Arslan, G. Akin, Ş.N. Karuk Elmas, I. Yilmaz, H.-G. Janssen, A. Kenar, Rapid detection of authenticity and adulteration of cold pressed black cumin seed oil: A comparative study of ATR–FTIR spectroscopy and synchronous fluorescence with multivariate data analysis, Food Control. 98 (2019). doi:10.1016/j.foodcont.2018.11.055.
- A. Kenar, B. Çiçek, F.N. Arslan, G. Akin, Ş.N. Karuk Elmas, I. Yilmaz, Electron Impact – Mass Spectrometry Fingerprinting and Chemometrics for Rapid Assessment of Authenticity of Edible Oils Based on Fatty Acid Profiling, Food Analytical Methods. 12 (2019), 1369–1381.
- G. Akin, Ş.N. Karuk Elmas, F.N. Arslan, İ. Yılmaz, A. Kenar, Chemometric classification and quantification of cold pressed grape seed oil in blends with refined soybean oils using attenuated total reflectance–mid infrared (ATR–MIR) spectroscopy, LWT - Food Science and Technology. 100 (2019) 126–137. doi:10.1016/j.lwt.2018.10.046.
- F.N. Arslan, F. Çağlar, Attenuated Total Reflectance – Fourier Transform Infrared (ATR – FTIR) Spectroscopy Combined with Chemometrics for Rapid Determination of Cold-Pressed Wheat Germ Oil Adulteration, Food Analytical Methods. 12 (2019), 355–370.
- A. Sayago, D. Garcia-Gonzalez, M. Morales, R. Aparicio, Detection of the Presence of Refined Hazelnut Oil in Refined Olive Oil by Fluorescence Spectroscopy, Journal of Agricultural and Food Chemistry. 55 (2007), 2068–2071.
- E. Sıkorska, A. Gliszczynska-Swiglo, I. Khmelinskii, M. Sıkorski, Synchronous Fluorescence Spectroscopy of Edible Vegetable Oils . Quantification of Tocopherols, Journal of Agricultural and Food Chemistry. 53 (2005), 6988–6994.
- E. Guzmán, V. Baeten, J. Antonio, F. Pierna, J.A. García-mesa, Evaluation of the overall quality of olive oil using fluorescence spectroscopy, Food Chemistry. 173 (2015), 927–934. doi:10.1016/j.foodchem.2014.10.041.
- P.B. Oldham, M.E. Mccarroll, L.B. Mcgown, I.M. Warner, N. Carolina, Molecular Fluorescence , Phosphorescence , and Chemiluminescence Spectrometry, Analytical Chemistry. 72 (2000), 197–210. doi:10.1021/a1000017p.
- K.I. Poulli, G.A. Mousdis, C. Georgio, Synchronous fluorescence spectroscopy for quantitative determination of virgin olive oil adulteration with sunflower oil, Analytical Bioanalytical Chemistry. 386 (2006), 1571–1575. doi:10.1007/s00216-006-0729-2.
- H. Tumay, U. Tamer, A. Berkkan, I. Hakki, Synchronous fluorescence spectroscopy for determination of tahini adulteration, Talanta. 167 (2017), 557–562.
- B. Li, H. Wang, Q. Zhao, J. Ouyang, Y. Wu, Rapid detection of authenticity and adulteration of walnut oil by FTIR and fluorescence spectroscopy : A comparative study, Food Chemistry. 181 (2015), 25–30. doi:10.1016/j.foodchem.2015.02.079.
- F. Ge, C. Chen, D. Liu, S. Zhao, Rapid Quantitative Determination of Walnut Oil Adulteration with Sunflower Oil Using Fluorescence Spectroscopy, Food Analytical Methods. 7 (2014), 146–150. doi:10.1007/s12161-013-9610-z.
- K.I. Poullı, N. V. Chantzos, G.A. Mousdıs, C.A. Georgıou, Synchronous Fluorescence Spectroscopy : Tool for Monitoring Thermally Stressed Edible Oils, Journal of Agricultural and Food Chemistry. 57 (2009), 8194–8201. doi:10.1021/jf902758d.
- Ş.N. Karuk Elmas, F.N. Arslan, G. Akin, A. Kenar, H. Janssen, I. Yilmaz, Synchronous fluorescence spectroscopy combined with chemometrics for rapid assessment of cold – pressed grape seed oil adulteration : Qualitative and quantitative study, Talanta. 196 (2019), 22–31. doi:10.1016/j.talanta.2018.12.026.
Kemometrik Veri Analiz Yaklaşımına Dayalı Senkron Floresans Spektroskopi Yöntemi: Mut (Mersin) Yöresi Zeytinyağları ve Rafine Yenilebilir Yağlarda Tağşiş Tespiti
Year 2023,
Volume: 5 Issue: 2, 278 - 287, 31.12.2023
Fatma Nur Arslan
,
İsmail Varlı
Abstract
Bu çalışma, Mut (Mersin) bölgesinden iki farklı hasat döneminde (2019 ve 2020 Ekim) elde edilen ekstra saf sızma zeytinyağı (VOO) ve farklı markalara ait rafine yemeklik yağ numunelerinde tağşiş/sahtecilik durumu hakkında fikir edinmeyi amaçlamaktadır. Araştırmayı gerçekleştirmek için senkron floresans (SyF) spektroskopisine dayalı analitik yaklaşım, PCA ve SIMCA kemometrik veri analiz yöntemi ile kullanılmıştır. SyF verileri 200–800 nm emisyon bölgesinde elde edilmiş ve uyarma/emisyon monokromatörleri senkronize şekilde kullanılmıştır. Saf VOO ve farklı türdeki yağ numuneleri için elde edilen veriler; PCA ve SIMCA çok değişkenli veri modellemeleri ile analiz edilmiştir. Elde edilen PCA skor grafiklerinde; yağ türlerinin ve farklı hasat zamanlarına ait zeytinyağı örneklerinin sınıflandırma yeteneğinin oldukça yüksek olduğu; SIMCA modellemelerinde ise VOO numunelerinin diğer yağ türlerinden %100 farklı bir grupta sınıflandırılabildiği tespit edilmiştir. Sonuç olarak SyF spektroskopisi kemometrik analiz yöntemleri ile birleştirildiğinde hız ve maliyet açısından oldukça avantajlı bir yöntem olup, zahmetli numune ön işlemleri ve kimyasal kullanımını ortadan kaldırarak büyük kolaylık sağlamaktadır.
Supporting Institution
The study is financially supported by the Scientific Research Project Center of KMU with a project number 23–YL–20.
Thanks
The authors wish to acknowledge the Scientific Research Project Center of KMU due to their financial support. The study and a part of master thesis titled ''Development of Simple and Rapid Synchronous Fluorescence Spectroscopy Methods based on Chemometric Data Analysis Approach for the Classification and Adulteration of Olive Oils in Mut (Mersin) Region''.
References
- F.N. Arslan, ATR–FTIRspectroscopy combined with chemometrics for rapid classification of extra virgin olive oils and edible oils from different cultivars available on the Turkish markets, Eskişehir Technical University Journal of Science and Technology A- Applied Sciences and Engineering. 19 (2018), 926–947. doi:10.18038/aubtda.425374.
- I. Gouvinhas, J.M.M.M. De Almeida, T. Carvalho, N. Machado, A.I.R.N.A. Barros, Discrimination and characterisation of extra virgin olive oils from three cultivars in different maturation stages using Fourier transform infrared spectroscopy in tandem with chemometrics, Food Chemistry. 174 (2015), 226–232.
- G. Yildiz, T. Huseyin, Quantification of soybean oil adulteration in extra virgin olive oil using portable raman spectroscopy, Food Measurement and Charecterization. 11 (2017), 523–529. doi:10.1007/s11694-016-9419-8.
- İ. Varlı, Development of Simple and Rapid Synchronous Fluorescence Spectroscopy Methods based on Chemometric Data Analysis Approach for the Classification and Adulteration of Olive Oils in Mut (Mersin) Region, Master Thesis, Karamanoglu Mehmetbey University Institute of Science, Department of Chemistry, Karaman (2022).
- M.K. Demir, N. Bilgiçli, S. Türker, B. Demir, Farklı Stabilizasyon İşlemleri Uygulanmış Buğday Ruşeymlerinin Depolama Özellikleri, Necmettin Erbakan University Journal of Science and Engineering. 2 (2019), 67–75.
- M. Bevilacqua, R. Bucci, A.D. Magrì, A.L. Magrì, F. Marini, Tracing the origin of extra virgin olive oils by infrared spectroscopy and chemometrics: A case study, Analytica Chimica Acta. 717 (2012), 39–51. doi:10.1016/j.aca.2011.12.035.
- Lerma-Garcia, G. Ramis-ramos, J.J. Martinez-Tellez, Simo-Alfonso, Authentication of extra virgin olive oils by Fourier-transform infrared spectroscopy, Food Chemistry. 118 (2010), 78–83. doi:10.1016/j.foodchem.2009.04.092.
- G. Ozulku, R.M. Yildirim, O.S. Toker, S. Karasu, M.Z. Durak, Rapid detection of adulteration of cold pressed sesame oil adultered with hazelnut , canola , and sun fl ower oils using ATR-FTIR spectroscopy combined with chemometric, Food Control. 82 (2017), 212–216.
- P. De, A. Dominguez-vidal, J.M. Bosque-sendra, A. Ruiz-medina, L. Cuadros-rodríguez, M.J. Ayora-cañada, Olive oil assessment in edible oil blends by means of ATR-FTIR and chemometrics, Food Control. 23 (2012), 449–455. doi:10.1016/j.foodcont.2011.08.013.
- F. Mabood, R. Boqué, R. Folcarelli, O. Busto, A. Al-harrasi, J. Hussain, Thermal oxidation process accelerates degradation of the olive oil mixed with sunflower oil and enables its discrimination using synchronous fluorescence spectroscopy and chemometric analysis, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 143 (2015), 298–303. doi:10.1016/j.saa.2015.01.119.
- A. Dankowska, M. Małecka, W. Kowalewski, Application of synchronous fluorescence spectroscopy with multivariate data analysis for determination of butter adulteration, International Journal of Food Science and Technology. 49 (2014), 2628–2634. doi:10.1111/ijfs.12594.
- J. Cao, C. Li, R. Liu, X. Liu, Y. Fan, Z. Deng, Combined Application of Fluorescence Spectroscopy and Chemometrics Analysis in Oxidative Deterioration of Edible Oils, Food Analytical Methods. 10 (2017), 649–658. doi:10.1007/s12161-016-0587-2.
- K. Poulli, N. V Chantzos, G.A. Mousdis, C.A. Gorgiou, Synchronous Fluorescence Spectroscopy : Tool for Monitoring Thermally Stressed Edible Oils, Journal of Agricultural and Food Chemistry. 57 (2009), 8194–8201. doi:10.1021/jf902758d.
- F.N. Arslan, G. Akin, Ş.N. Karuk Elmas, I. Yilmaz, H.-G. Janssen, A. Kenar, Rapid detection of authenticity and adulteration of cold pressed black cumin seed oil: A comparative study of ATR–FTIR spectroscopy and synchronous fluorescence with multivariate data analysis, Food Control. 98 (2019). doi:10.1016/j.foodcont.2018.11.055.
- A. Kenar, B. Çiçek, F.N. Arslan, G. Akin, Ş.N. Karuk Elmas, I. Yilmaz, Electron Impact – Mass Spectrometry Fingerprinting and Chemometrics for Rapid Assessment of Authenticity of Edible Oils Based on Fatty Acid Profiling, Food Analytical Methods. 12 (2019), 1369–1381.
- G. Akin, Ş.N. Karuk Elmas, F.N. Arslan, İ. Yılmaz, A. Kenar, Chemometric classification and quantification of cold pressed grape seed oil in blends with refined soybean oils using attenuated total reflectance–mid infrared (ATR–MIR) spectroscopy, LWT - Food Science and Technology. 100 (2019) 126–137. doi:10.1016/j.lwt.2018.10.046.
- F.N. Arslan, F. Çağlar, Attenuated Total Reflectance – Fourier Transform Infrared (ATR – FTIR) Spectroscopy Combined with Chemometrics for Rapid Determination of Cold-Pressed Wheat Germ Oil Adulteration, Food Analytical Methods. 12 (2019), 355–370.
- A. Sayago, D. Garcia-Gonzalez, M. Morales, R. Aparicio, Detection of the Presence of Refined Hazelnut Oil in Refined Olive Oil by Fluorescence Spectroscopy, Journal of Agricultural and Food Chemistry. 55 (2007), 2068–2071.
- E. Sıkorska, A. Gliszczynska-Swiglo, I. Khmelinskii, M. Sıkorski, Synchronous Fluorescence Spectroscopy of Edible Vegetable Oils . Quantification of Tocopherols, Journal of Agricultural and Food Chemistry. 53 (2005), 6988–6994.
- E. Guzmán, V. Baeten, J. Antonio, F. Pierna, J.A. García-mesa, Evaluation of the overall quality of olive oil using fluorescence spectroscopy, Food Chemistry. 173 (2015), 927–934. doi:10.1016/j.foodchem.2014.10.041.
- P.B. Oldham, M.E. Mccarroll, L.B. Mcgown, I.M. Warner, N. Carolina, Molecular Fluorescence , Phosphorescence , and Chemiluminescence Spectrometry, Analytical Chemistry. 72 (2000), 197–210. doi:10.1021/a1000017p.
- K.I. Poulli, G.A. Mousdis, C. Georgio, Synchronous fluorescence spectroscopy for quantitative determination of virgin olive oil adulteration with sunflower oil, Analytical Bioanalytical Chemistry. 386 (2006), 1571–1575. doi:10.1007/s00216-006-0729-2.
- H. Tumay, U. Tamer, A. Berkkan, I. Hakki, Synchronous fluorescence spectroscopy for determination of tahini adulteration, Talanta. 167 (2017), 557–562.
- B. Li, H. Wang, Q. Zhao, J. Ouyang, Y. Wu, Rapid detection of authenticity and adulteration of walnut oil by FTIR and fluorescence spectroscopy : A comparative study, Food Chemistry. 181 (2015), 25–30. doi:10.1016/j.foodchem.2015.02.079.
- F. Ge, C. Chen, D. Liu, S. Zhao, Rapid Quantitative Determination of Walnut Oil Adulteration with Sunflower Oil Using Fluorescence Spectroscopy, Food Analytical Methods. 7 (2014), 146–150. doi:10.1007/s12161-013-9610-z.
- K.I. Poullı, N. V. Chantzos, G.A. Mousdıs, C.A. Georgıou, Synchronous Fluorescence Spectroscopy : Tool for Monitoring Thermally Stressed Edible Oils, Journal of Agricultural and Food Chemistry. 57 (2009), 8194–8201. doi:10.1021/jf902758d.
- Ş.N. Karuk Elmas, F.N. Arslan, G. Akin, A. Kenar, H. Janssen, I. Yilmaz, Synchronous fluorescence spectroscopy combined with chemometrics for rapid assessment of cold – pressed grape seed oil adulteration : Qualitative and quantitative study, Talanta. 196 (2019), 22–31. doi:10.1016/j.talanta.2018.12.026.