Microwave hydrodistillation of Poncirus trifoliata peels and essential oil profile: Greenness assessment

Öz

The study aimed to determine the profile of the essential oil obtained by hydrodistillation (MHD) and classical steam distillation (SD) methods and the bioactive potential of the wastewater produced in this process. The chemical composition of the essential oils was analyzed by Gas Chromatography-Mass Spectrometry (GC-MS), while the total phenolic content (TPC), total flavonoid content (TFC), total proanthocyanidin (TPA) and total antioxidant capacity of the wastewater (aqueous phase) after distillation were determined by spectrophotometric methods. GC-MS analysis revealed that the main component of the essential oils obtained by both methods was limonene, but there were significant differences in the relative proportions of the components. The SD method yielded a higher proportion of monoterpene hydrocarbons (70.27%) and esters (8.59%), while the MHD method was more efficient in sesquiterpene hydrocarbons (14.06%) and oxygenated monoterpenes (2.10%). In wastewater analysis, the wastewater obtained by SD method showed higher antioxidant capacity (with CUPRAC and CERAC) and higher TPC and TFC values compared to MHD. In addition, MHD (0.53 points) was found to be slightly more environmentally friendly than SD (0.49 points) in terms of energy consumption and sample size in the greenness assessment using the AGREEprep tool. In conclusion, it can be concluded that post-distillation wastewater is also a valuable source of bioactive compounds and the choice of method should be based on the targeted compound profile and the requirements of the application.

Anahtar Kelimeler

• P. trifoliata
• wastewater
• antioxidant
• essential oil

Poncirus trifoliata kabuklarının mikrodalga hidrodistilasyonu ve uçucu yağ profili: Yeşillik değerlendirmesi

Öz

Çalışmanın amacı, hidrodistilasyon (MHD) ve klasik buhar distilasyonu (SD) yöntemleriyle elde edilen uçucu yağ profilini ve bu süreçte üretilen atık suyun biyoaktif potansiyelini belirlemektir. Uçucu yağların kimyasal bileşimi Gaz Kromatografisi-Kütle Spektrometresi (GC-MS) ile analiz edilirken, distilasyon sonrası atık suyun (sulu faz) toplam fenolik içeriği (TPC), toplam flavonoid içeriği (TFC), toplam proantosiyanidin (TPA) ve toplam antioksidan kapasitesi spektrofotometrik yöntemlerle belirlenmiştir. GC-MS analizi, her iki yöntemle elde edilen uçucu yağların ana bileşeninin limonen olduğunu, ancak bileşenlerin nispi oranlarında önemli farklılıklar olduğunu ortaya koymuştur. SD yöntemi daha yüksek oranda monoterpen hidrokarbonlar (%70,27) ve esterler (%8,59) verirken, MHD yöntemi seskiterpen hidrokarbonlar (%14,06) ve oksijenli monoterpenlerde (%2,10) daha etkili olmuştur. Atık su analizinde, SD yöntemiyle elde edilen atık su, MHD'ye kıyasla daha yüksek antioksidan kapasite (CUPRAC ve CERAC ile) ve daha yüksek TPC ve TFC değerleri göstermiştir. Ayrıca, AGREEprep aracı kullanılarak yapılan yeşillik değerlendirmesinde MHD'nin (0,53 puan) enerji tüketimi ve numune büyüklüğü açısından SD'den (0,49 puan) biraz daha çevre dostu olduğu görülmüştür. Sonuç olarak, damıtma sonrası atık suyun da değerli bir biyoaktif bileşik kaynağı olduğu ve yöntem seçiminin hedeflenen bileşik profiline ve uygulamanın gerekliliklerine dayanması gerektiği sonucuna varılabilir.

Anahtar Kelimeler

• P.trifoliata
• atık su
• antioksidan
• uçucu yağ

Kaynakça

1. H.Y. Lee, S. W. Kim, Y.K. Kim, S.Y. Lee, M.Y. Yoon, Protective effect of Poncirus trifoliata fruit extracts against gastric ulcer in rats, Food Sci Biotechnol, 20, 2011, 1097–1102.
2. Y. Zhang, Y. Li, Y. Wang, X. Zhang, H. Zhang, Chemical constituents and pharmacological activities of Poncirus trifoliata (L.) Raf.: A review. Phytochem. Rev., 19, 2020, 97–119.
3. H.J. Kim, J.H. Kim, H.Y. Park, J.Y. Kim, H.J. Lee, Antioxidant and antimicrobial activities of extracts from Poncirus trifoliata fruit, Korean J Food Sci Technol, 46, 2014, 351–357.
4. A. Bocco, M. E. Cuvelier, H. Richard, C.Berset, Antioxidant activity and phenolic composition of citrus peel and seed extracts. J Agric Food Chem, 46, 1998, 2123-2129.
5. Z. Wang, Q. Shang, W. Wang, X. Feng, Microwave-assisted extraction and liquid chromatography/mass spectrometry anaysis of flavonoids from grapefruit peel. J Food Process Eng, 34, 2011, 844–859.
6. A. Di Mauro, B. Fallico, A. Passerini, E.Maccarone, Waste water from citrus processing as a source of hesperidin by concentration on styrene− divinylbenzene resin. J Agric Food Chem, 48, 2000, 2291-2295.
7. B.B. Li, B. Smith, M.M Hossain, Extraction of phenolics from citrus peels: I. Solvent extraction method, Sep Purif Technol, 48, 2006, 182-188.
8. M. J. Ko, C. I. Cheigh, M. S. Chung, Relationship analysis between flavonoids structure and subcritical water extraction (SWE). Food Chem, 143, 2014, 147-155.

9. A.N. Giannuzzo, H. J. Boggetti, M. A. Nazareno, H. T. Mishima, Supercritical fluid extraction of naringin from the peel of Citrus paradisi. Phytochem Anal, 14, 2003, 221-223.
10. P.A. Uwineza, A. Waśkiewicz, Recent advances in supercritical fluid extraction of natural bioactive compounds from natural plant materials, Molecules 2020, 25(17), 3847.
11. A. Krakowska-Sieprawska, A. Kiełbasa, K. Rafińska, M. Ligor, B. Buszewski, Modern methods of pre-treatment of plant material for the extraction of bioactive compounds, Molecules, 27, 2022, 730.
12. M. Boukroufa, C. Boutekedjiret, L. Petigny, N. Rakotomanomana, F. Chemat, Bio-refinery of orange peels waste: A new concept based on integrated green and solvent free extraction processes using ultrasound and microwave techniques to obtain essential oil, polyphenols and pectin. Ultrason. Sonochem., 24, 2015, 72-79.
13. W. Routray, V. Orsat, Microwave-assisted extraction of flavonoids: A review. Food Bioproc. Tech., 5, 2012, 409–424.
14. F. Chemat, N. Rombaut, A. G. Sicaire, A. Meullemiestre, A. S. Fabiano-Tixier, M. Abert-Vian, Ultrasound assisted extraction of food and natural products. Mechanisms, techniques, combinations, protocols and applications. A review. Ultrason. Sonochem., 34, 2017, 540–560.
15. J. Dai, R. J. Mumper, Plant phenolics: Extraction, analysis and their antioxidant and anticancer properties. Molecules, 15, 2010, 7313–7352.
16. S. Fan, J. Chang, Y. Zong, G. Hu, J. Jia, GC-MS analysis of the composition of the essential oil from Dendranthema indicum Var. Aromaticum using three extraction methods and two columns. Molecules, 23, 2018, 576.
17. L.M. Magalhães, F. Santos, M. A. Segundo, S. Reis, J.L. Lima, Rapid microplate high-throughput methodology for assessment of Folin-Ciocalteu reducing capacity. Talanta, 83, 2010, 441-447.
18. J. Zhishen, T. Mengcheng, W. Jianming, The determination of flavonoid contents in mulberry and their scavenging effects on superoxide radicals. Food Chem, 64, 1999, 555-559.
19. J. Zurita, M. E. Díaz-Rubio, F. Saura-Calixto, Improved procedure to determine non-extractable polymeric proanthocyanidins in plant foods. Int J Food Sci Nutr 63, 2012, 936–939.
20. R. Apak, K. Güçlü, B. Demirata, M. Özyürek, S. Çelik, B. Bektaşoğlu, D. Özyurt, Comparative evaluation of various total antioxidant capacity assays applied to phenolic compounds with the CUPRAC assay. Molecules, 12, 2007, 1496-1547.
21. D. Ozyurt, B. Demirata, R. Apak, Modified cerium (IV)-based antioxidant capacity (CERAC) assay with selectivity over citric acid and simple sugars. J. Food Compos. Anal., 23, 2010, 282-288.
22. R. Re, N. Pellegrini, A. Proteggente, A. Pannala, M. Yang, C. Rice-Evans, Antioxidant activity applying an improved ABTS radical cation decolorization assay. Free Radic. Biol. Med., 26, 1999, 1231-1237.
23. Y. Zhang, X. Zhao, Q. Yang, Li, Y., X. Liu, M. Huang, Recovery and utilization of phenolic compounds from distillation wastewater of essential oil plants: A review. Ind Crops Prod, 170, 2021, 113753.
24. Y.J. Fu, Y.G. Zu, L.Y. Chen, X.H. Shi, Z. Wang, S. Sun, T. Efferth, Antioxidant properties of waste residues from vine tea (Ampelopsis grossedentata) extraction. Afr. J. Biotechnol., 9, 2010, 7248–7253.
25. Y. Liu, Z. Liu, C. Wang, Q. Zha, C. Lu, Z. Song, A. Lu, Study on essential oils from four species of Zhishi with gas chromatography–mass spectrometry. Chem. Cent. J., 8, 2014, 22.
26. F. Papa, F. Maggi, K. Cianfaglione, G. Sagratini, G. Caprioli, S. Vittori, Volatile profiles of flavedo, pulp and seeds in Poncirus trifoliata fruits. J Sci Food Agric 94, 2014, 2874–2887.
27. M. E. Lucchesi, F. Chemat, J. Smadja, Solvent-free microwave extraction of essential oil from aromatic herbs: Comparison with conventional hydro-distillation. J. Chromatogr. A, 1043, 2004, 323–327.
28. V. Mandal, Y. Mohan, S.Hemalatha, Microwave assisted extraction – an innovative and promising extraction tool for medicinal plant research. Phcog Rev, 5, 2011, 7.
29. A. Rahman, S. M. Al-Reza, J. I. Yoon, S. C. Kang, In vitro inhibition of foodborne pathogens by volatile oil and organic extracts of Poncirus trifoliata seeds, J Sci Food Agric, 89, 2009, 876–881.
30. C. Starkenmann, Y. Niclass, S. Escher, Volatile organic sulfur-containing constituents in Poncirus trifoliata fruit peel. J Agric Food Chem, 55, 2007, 4511–4517.
31. K. Boztaş, Y. C. Gercek, G. Türer, D. Canlı, S. Bayram, S. Çelik, N. Ecem Bayram, Microwave hydrodistillation of Pelargonium graveolens L'Her leaves: Essential oil profile, phytochemical composition of wastewater, histo-anatomical structure. J. Essent. Oil-Bear. Plants, 27, 2024, 659-677.
32. L. Zhang, W. Bai, L. Zhou, C. Li, Comparative evaluation of extraction technologies on the chemical composition and antioxidant activity of essential oils from citrus peels. Ind Crops Prod, 191, 2023, 116066.
33. W. Wojnowski, M. Tobiszewski, F. Pena-Pereira, E. Psillakis, AGREEprep–analytical greenness metric for sample preparation. TrAC Trends Anal. Chem. 149, 2022, 116553.