Zeytin Posasından Türetilen Manyetik Biyochar ile Sudan Tetrasiklinin Etkin Giderimi

Yıl 2025, Cilt: 7 Sayı: 3, 268 - 281, 30.09.2025

Burcu Kabak

https://doi.org/10.51435/turkjac.1699857

Öz

Yaygın olarak kullanılan bir antibiyotik olan tetrasiklinin (TC) kontrolsüz salınımı, kalıcılığı ve antibiyotik direncine katkıda bulunması nedeniyle su ekosistemleri için önemli bir tehdit oluşturmaktadır. Bu çalışmada, zeytin posasından (OBC) biyokömür adsorban sentezlenmiş ve su içerisindeki TC giderim verimliliğini artırmak amacıyla manyetik olarak modifiye edilmiştir (MOBC). Adsorbanlar, FTIR, XRD, BET, TGA ve FESEM-EDX yöntemleriyle kapsamlı şekilde karakterize edilmiştir. pH, dozaj, temas süresi, sıcaklık ve konsantrasyon gibi parametrelerin giderim performansı üzerindeki etkilerini değerlendirmek için seri adsorpsiyon deneyleri gerçekleştirilmiştir. MOBC, artırılmış yüzey alanı, gözeneklilik ve manyetik özellikleri sayesinde ham biyokömüre göre daha yüksek adsorpsiyon kapasitesi (25 °C’de 248,77 mg/g) ve daha hızlı adsorpsiyon kinetiği sergilemiştir. Adsorpsiyon süreci, yalancı birinci dereceden kinetik modele uymuş ve en iyi Langmuir izoterm modeli ile açıklanmıştır. Termodinamik analiz, işlemin kendiliğinden gerçekleşen ve ekzotermik olduğunu, adsorpsiyon mekanizmasında ise fiziksel etkileşimlerin baskın rol oynadığını ortaya koymuştur. MOBC, NaOH kullanılarak yüksek desorpsiyon verimi ile umut verici bir yeniden kullanılabilirlik göstermiş ve gerçek su örneklerinde de önemli performansını korumuştur. Bu sonuçlar, MOBC’nin çevresel iyileştirme uygulamalarında farmasötik kirleticilerin giderimi için düşük maliyetli, sürdürülebilir ve etkili bir adsorban olduğunu göstermektedir.

Anahtar Kelimeler

Biyokömür , Zeytin posası , Tetrasiklin giderimi , Manyetik fonksiyonelleştirme , Su arıtma , Adsorpsiyon

Magnetic biochar derived from olive pomace for efficient tetracycline removal from water

Öz

The uncontrolled release of tetracycline (TC), a widely used antibiotic, poses a significant threat to aquatic ecosystems owing to its persistence and contribution to antibiotic resistance. In this study, a biochar adsorbent was synthesised from olive pomace (OBC) and further magnetically modified (MOBC) to enhance its removal efficiency for TC in water. The adsorbents were extensively characterised using FTIR, XRD, BET, TGA, and FESEM-EDX. Batch adsorption experiments were conducted to evaluate the influence of pH, dosage, contact time, temperature, and concentration on removal performance. MOBC exhibited a superior adsorption capacity (248.77 mg/g at 25 °C) and faster kinetics than raw biochar, mainly due to improved surface area, porosity, and magnetic functionality. The adsorption process followed pseudo-first-order kinetics and was best described using the Langmuir isotherm model. Thermodynamic analysis revealed that the process is spontaneous and exothermic, with physical interactions dominating the adsorption mechanism. The MOBC demonstrated promising reusability with high desorption efficiency using NaOH and maintained substantial performance in real water matrices. These results highlight MOBC as a low-cost, sustainable, and efficient adsorbent for pharmaceutical contaminant removal in environmental remediation applications.

Anahtar Kelimeler

Olive Pomace , Tetracycline Removal , Magnetic Functionalization , Water Treatment , Biochar , Adsorption

Kaynakça

• X. Zhang, D. Zhen, F. Liu, R. Chen, Q. Peng, Z. Wang, An achieved strategy for magnetic biochar for removal of tetracyclines and fluoroquinolones: Adsorption and mechanism studies, Bioresour Technol, 369, 2023, 128440.
• B. Kabak, Synthesis and application of Tb-MOF for efficient fluorescence detection and removal of tetracycline from aqueous environments, J Mol Struct, 1322, 2025, 140348.
• Y. Amangelsin, Y. Semenova, M. Dadar, M. Aljofan, G. Bjørklund, The impact of tetracycline pollution on the aquatic environment and removal strategies, Antibiotics, 12, 2023, 440.
• N.T. Huong, H.T. Huyen, T.Q. Phong, Conjugation of tetracycline with carrier proteins and production of its polyclonal antibody for the development of rapid test, Vietnam J Sci Technol, 62 (1), 2024, 23-34.
• J. Jaroszewski, N. Mamun, K. Czaja, Bidirectional interaction between tetracyclines and gut microbiome, Antibiotics, 12, 2023, 1438.
• J. Wang, P. Li, Y. Zhao, X. Zeng, Nb/N Co-Doped layered perovskite Sr2TiO4: preparation and enhanced photocatalytic degradation tetracycline under visible light, Int. J. Mol. Sci. 2022, 23, 10927.
• L. Qian, B. Chen, Dual role of biochars as adsorbents for aluminum: The effects of oxygen-containing organic components and the scattering of silicate particles, Environ. Sci. Technol, 47(15), 2013, 8759-8768.
• Wang, H. Zhao, J. Liu, X. Wang, J. Li, E. Shi, C. Wang, J. Yang, Z. Zhang, A study on and adsorption mechanism of ammonium nitrogen by modified corn straw biochar, R Soc Open Sci, 10, 2023, 221535.
• P. He, Q. Yu, H. Zhang, L. Shao, F. Lü, Removal of Copper (II) by biochar mediated by dissolved organic matter, Sci, Rep, 7, 2017, 7091.
• L. Qian, B. Chen, Interactions of aluminum with biochars and oxidized biochars: Implications for the biochar aging process, J Agric Food Chem, 61(36), 2013, 8174-8181.
• X. Zhang, J. Hou, T. Cai, S. Zhang, L. Shen, Q. Zhang, Functionalized construction of highly aromatic condensed graphitized biochar for tetracycline adsorption, Environ Technol Innov, 37, 2025, 104002.
• L. Lin, L. Ning, S. Chen, B. Wang, H. Zhuang, X. Jing, Q. Li, Ultra-large adsorption capacity for tetracycline by defatted Schizochytrium limacinum residue biochar, Algal Res, 88, 2025, 104011.
• G. Loebsack, K.K.C. Yeung, F. Berruti, N.B. Klinghoffer, Impact of biochar physical properties on adsorption mechanisms for removal of aromatic aqueous contaminants in water. Biomass Bioenergy 194, 2025, 107617.
• A. Bano, B. Prasad, H. Dave, K.S. Prasad, A mechanistic insight on non-steroidal anti-inflammatory drug, ketoprofen removal from pharmaceutical wastewater by a magnetic biochar: Batch and fixed bed adsorption studies, Inorg Chem Commun, 173, 2025, 113802.
• A. Durán, J.M. Monteagudo, J. Delgado, Degradation of antipyrine in water with activated persulfate aided with biochar of olive pomace, J Environ Manage, 368, 2024, 122159.
• I, Rabichi, K, Ezzahi, F.E. Yaacoubi, Z. Izghri, K. Ennaciri, A. Ounas, A. Yaacoubi, A. Baçaoui, M. Hafidi, L. El Fels, Evaluating the fixed-bed column adsorption capacity of olive pomace biochar activated with KOH and H₃PO₄ for olive mill wastewater treatment: Insights from TOC and HPLC analysis. Chemosphere, 377, 2025, 144356.
• L.M. Ruiz, M. Fernández, A. Genaro, J. Martín-Pascual, M. Zamorano, Multi-parametric analysis based on physico-chemical characterization and biochemical methane potential estimation for the selection of industrial wastes as co-substrates in anaerobic digestion, Energies 16, 2023, 5444.
• C. Nasopoulou, K. Lytoudi, I. Zabetakis, Evaluation of olive pomace in the production of novel broilers with enhanced in vitro antithrombotic properties, Eur J Lipid Sci Technol, 120(4), 2018, 1700290.
• A. Ncube, G. Fiorentino, C. Panfilo, M. De Falco, S. Ulgiati, Circular economy paths in the olive oil industry: a Life Cycle Assessment look into environmental performance and benefits, Int J Life Cycle Assess, 29, 2024, 1541–1561.
• C. Romero, E. Medina, M. A. Mateo, M. Brenes, New by-products rich in bioactive substances from the olive oil mill processing, J Sci Food Agric, 98, 2018, 225–230.
• N. Montegiove, A.M. Gambelli, E. Calzoni, A. Bertoldi, D. Puglia, C. Zadra, C. Emiliani, G. Gigliotti, Biogas production with residuals deriving from olive mill wastewater and olive pomacewastes: quantification of produced energy, spent energy, and process efficiency, Agronomy 14, 2024, 531.
• J.D. Palmeira, D. Araújo, C.C. Mota, R.C. Alves, M.B.P.P. Oliveira, H.M.N. Ferreira, Fermentation as a strategy to valorize olive pomace, a by-product of the olive oil industry, Fermentation, 9, 2023, 442.
• M. Puig-Gamero, J.R. Trapero, P. Sánchez, L. Sanchez- Silva, Is methanol synthesis from co-gasification of olive pomace and petcoke economically feasible?, Fuel, 278, 2020, 118284.
• G. Espadas-Aldana, P. Guaygua-Amaguaña, C. Vialle, J.-P. Belaud, P. Evon, C. Sablayrolles, Life cycle assessment of olive pomace as a reinforcement in polypropylene and polyethylene biocomposite materials: A new perspective for the valorization of this agricultural by-product, Coatings, 11, 2021, 525.
• M. Centrone, M. D’Agostino, G. Difonzo, A. De Bruno, A. Di Mise, M. Ranieri, C. Montemurro, G. Valenti, M. Poiana, F. Caponio, G. Tamma, Antioxidant efficacy of olive by-product extracts in human Colon HCT8 Cells, Foods, 10, 2021,11.
• D.L.C. Rodrigues, A.C.F.P. Fuhr, J.A. Guido, C.F. de Azevedo, A.M. Rangel, G.L. Dotto, S.Y. Alomar, F.M. Machado, Olive biomass-derived magnetic activated biochar for ciprofloxacin removal: Integrated kinetic, isotherm, thermodynamic, and spectroscopic analysis. Sep Purif Technol, 360, 2025, 131014.
• T.M. Huggins, A. Haeger, J.C. Biffinger, Z.J. Ren, Granular biochar compared with activated carbon for wastewater treatment and resource recovery, Water Res, 94, 2016, 225-232.
• E. Gul, K.A.B. Alrawashdeh, O. Masek, Ø. Skreiberg, A. Corona, M. Zampilli, L. Wang, P. Samaras, Q. Yang, H. Zhou, P. Bartocci, F. Fantozzi, Production and use of biochar from lignin and lignin-rich residues (such as digestate and olive stones) for wastewater treatment, J Anal Appl Pyrolysis, 158, 2021, 105263.
• A. Hmid, D. Mondelli, S. Fiore, F.P. Fanizzi, Z. Al Chami, S. Dumontet, Production and characterization of biochar from three-phase olive mill waste through slow pyrolysis, Biomass & Bioenergy, 71, 2014, 330e339.
• N.S. Hassan, A.A. Jalil, N.M. Izzuddin, M.B. Bahari, A.H. Hatta, R.M. Kasmani, N. Norazahar, Recent advances in lignocellulosic biomass-derived biochar-based photocatalyst for wastewater remediation, J Taiwan Inst Chem Eng, 163, 2024, 105670.
• G. Peer, H. Azaizeh, E. Kurzbaum, B. Shahar, N. Mattar, S.P. Azerra, Valorization of olive mill solid waste-derived biochar: An efficient approach for simultaneous adsorption and oxidation of micropollutant in surface water, J Water Process Eng, 56, 2023, 104461.
• S. Nand, P.P. Singh, S. Verma, S. Mishra, A. Patel, S. Shukla, Pankaj Kumar Srivastava, Biochar for mitigating pharmaceutical pollution in wastewater: A sustainable solution, Sci Total Environ, 966, 2025, 178743.
• O. Bayram, E. Köksal, E. Moral, F. Göde, E. Pehlivan, Efficient decolorization of cationic dye (malachite green) by natural-based biosorbent (nanomagnetic Sophora Japonica fruit seed biochar), J Disper Sci Technol, 45, 2022, 117-128.
• O. Bayram, E. Moral, E. Köksal, F. Göde, E. Pehlivan, Removal of methyl blue and malachite green from water using biodegradable magnetic Tamarindus Indica fruit seed biochar: Characterization, equilibrium study, modelling and thermodynamics, SCENV, 3, 2023, 100023.
• S. Mortazavian, S.E.H. Murph, J. Moon, Biochar nanocomposite as an inexpensive and highly efficient carbonaceous adsorbent for hexavalent chromium removal, Materials 15, 2022, 6055.
• P. Sun, C. Hui, R.A. Khan, J. Du, Q. Zhang, Y.H. Zhao, Efficient removal of crystal violet using Fe₃O₄-coated biochar: The role of the Fe₃O₄ nanoparticles and modeling study of their adsorption behavior, Sci Rep, 5, 2025, 12638.
• N.A. Guel-Nájar, J.C. Rios-Hurtado, E.M. Muzquiz-Ramos, G.I. Dávila-Pulido, A.A. González-Ibarra, A.M. Pat-Espadas, Magnetic biochar obtained by chemical coprecipitation and pyrolysis of corn cob residues: Characterization and methylene blue adsorption, Materials, 16, 2023, 3127.
• C. Lomenech, Ch. Hurel, L. Messina, M. Schembri, P. Tosi, F. Orange, F. Georgi, A. Mija & P. Kuzhir, A humins-derived magnetic biochar for water purification by adsorption and magnetic separation, Waste Biomass Valori, 12, 2021, 6497–6512.
• P.B. Hassan, R.O. Rasheed, K. Zargoosh, Cadmium and lead removal from aqueous solution using magnetite nanoparticles biofabricated from Portulaca oleracea leaf extract, J Nanomater, 2022(1), 2022, 1024554.
• A. Azizi, Green synthesis of Fe₃O₄ nanoparticles and its application in preparation of Fe₃O₄/cellulose magnetic nanocomposite: A suitable proposal for drug delivery systems, J Inorg Organomet P, 30, 2020, 3552–3561.
• F. Ghasemy-Piranloo, F. Bavarsiha, S. Dadashian, Tribological properties of core/shell Fe₃O₄/TiO₂ composites as additives in base oil, J Sol-Gel Sci Technol, 103, 2022, 908–920.
• D. Devanand, R. Khatkar, S. Nahar, S. Nagpal, Remediation of chlorpyrifos by utilizing waste packaging wood as magnetic biochar, Remediation, 34, 2024, e21781.
• Y. Gu, Y. Xue, D. Zhang, Adsorption of aniline by magnetic biochar with high magnetic separation efficiency, Environ Pollut Bioavailab, 33 (1), 2021, 66–75.
• T. Ao, P. Kalita, C. Blada, N.P. Brown, K. Fulford, P. Gard, M. Geissel, H. Hanshaw, M. Montoya, S. Payne, E. Scoglietti, A. Smith, C.S. Speas, J.L. Porter, C.T. Seagle, Exploring the high-pressure phases of carbon through X-ray diffraction of dynamic compression experiments on Sandia’s Z pulsed power facility, Minerals 13, 2023, 1203.
• X. Liu, R. Han, X. Zhao, D. Ma, R. Han, Characterization of bio-char from pyrolysis of wheat straw and its evaluation on methylene blue adsorption, Desalin Water Treat, 40, 2012, 1–7.
• N. Strutynska, I. Zatovsky, N. Slobodyanik, A. Malyshenko, Y. Prylutskyy, O. Prymak, I. Vorona, S. Ishchenko, N. Baran, A. Byeda, A. Mischanchuk, Preparation, characterization, and thermal transformation of poorly crystalline sodium- and carbonate-substituted calcium phosphate, Eur J Inorg Chem, 2015 (4), 2015, 622–629.
• Y. Zhang, X. Kang, J. Tan, R.L. Frost, Influence of calcination and acidification on structural characterization of Anyang anthracites, Energy Fuel, 27 (11), 2013,7191–7197.
• S.A.M. Zobir, S. Abu Bakar, S. Abdullah, Z. Zainal, S.H. Sarijo, M. Rusop, Raman spectroscopic study of carbon nanotubes prepared using Fe/ZnO–palm olein–chemical vapour deposition, J Nanomater, 2012(1), 2012, 451473.
• K. Kisu, E. Iwama, W. Naoi, P. Simon, K. Naoi, Electrochemical kinetics of nanostructure LiFePO₄/graphitic carbon electrodes, Electrochem Commun, 72, 2016, 10–14.
• V. Roungos, C.G. Aneziris, H. Berek, Novel Al₂O₃-C refractories with less residual carbon due to nanoscaled additives for continuous steel casting applications, Adv Eng Mater, 14 (4), 2012, 255–261.
• I.W. Suryawan, I.Y. Septiariva, E.N. Fauziah, B.S. Ramadan, F.D. Qonitan, N.L. Zahra, A. Sarwono, M.M. Sari, K.K. Ummatin, L.J. Wei, Municipal solid waste to energy: Palletization of paper and garden waste into refuse derived fuel, J Ecol Eng, 23 (4), 2022, 64–74.
• D. Aller, S. Bakshi, D.A. Laird, Modified method for proximate analysis of biochars, J Anal Appl Pyrol, 124, 2017, 335–342.
• Z. Shen, Y. Zhang, F. Jin, D.S. Alessi, Y. Zhang, F. Wang, O. McMillan, A. Al-Tabbaa, Comparison of nickel adsorption on biochars produced from mixed softwood and Miscanthus straw, Environ Sci Pollut Res, 25, 2018, 14626–14635.
• M.K. Rafiq, R.T. Bachmann, M.T. Rafiq, Z. Shang, S. Joseph, R. Long, Influence of pyrolysis temperature on physico-chemical properties of corn stover (Zea mays L.) biochar and feasibility for carbon capture and energy balance, PLoS ONE, 11 (6), 2016, e0156894.
• Y. Chen, L. Li, Q. Wen, R. Yang, Y. Zhao, X. Rao, J. Li, S. Xu, H. Song, Oxidative magnetic modification of pristine biochar assisted by ball-milling for removal of methylene blue and tetracycline in aqueous solution, Sustainability, 14, 2022, 9349.
• M. Idrees, S. Jeelani, V.K. Rangari, 3D printed sustainable biochar-recycled PET composite, ACS Sustain Chem Eng, 6 (10), 2018, 12331–12339.
• X. Zhang, X. Yang, X. Yuan, S. Tian, X. Wang, H. Zhang, L. Han, Effect of pyrolysis temperature on composition, carbon fraction and abiotic stability of straw biochars: correlation and quantitative analysis, Carbon Res, 1, 2022, 17.
• E.E. Oprescu, E.C. Enascuta, G. Vasilievici, N.D. Banu, I. Banu, Preparation of magnetic biochar for nitrate removal from aqueous solutions, React Kinet Mech Catal, 135, 2022, 2629–2642.
• J.M. Monteagudo, A. Duŕan, M. Alonso, A.-I. Stoica, Investigation of effectiveness of KOH-activated olive pomace biochar for efficient direct air capture of CO2, Sep Purif Technol, 352, 2025, 127997.
• A. Alcazar-Ruiz, S. Maisano, V. Chiodo, F. Urbani, F. Dorado, L. Sanchez-Silva, Enhancing CO2 capture performance through activation of olive pomace biochar: A comparative study of physical and chemical methods, SM&T, 42, 2024, e01177.
• M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing, Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report), Pure Appl Chem, 87 (9–10), 2015, 1051–1069.
• R, Şensoy, B, Kabak, E, Kendüzler, Kinetic and isothermal studies of naproxen adsorption from aqueous solutions using walnut shell biochar, React Kinet Mech Catal, 137, 2024, 1031–1049.