An Evaluation for Adsorption Behaviour and Mechanism of Methylene Blue on Peach Seeds: Isotherm, Kinetic and Thermodynamic Studies : An Evaluation for Adsorption Behaviour and Mechanism of Methylene Blue on Peach Seeds: Isotherm, Kinetic and Thermodynamic Studies

Ali Rıza Kul; Adnan Aldemir

Authors

Ali Rıza Kul Van Yüzüncü Yıl University, Faculty of Science, Chemistry Department, 65080, Van, Türkiye https://orcid.org/0000-0001-9331-775X
Adnan Aldemir Assoc.Prof.Dr. https://orcid.org/0000-0001-9884-0961

Keywords:

adsorption, isotherm, kinetic, thermodynamic, methylene blue

Abstract

In the present study, adsorbent prepared from peach seed (PSA) was used for the removal of Methylene Blue (MB), widely utilized dye from aqueous solutions. The influence of operational parameters, including initial MB concentration (20–120 mg L⁻¹), temperature (298–323 K), and contact time (10–180 min), was systematically examined. The removal efficiencies at the 40 mg L⁻¹ initial MB concentration were determined to be 63.9 %, 75.6 %, and 81.6 % at the 298 K, 308 K, and 323 K, respectively. The maximum adsorption capacity (qₘ) was achieved at 156.251 mg g⁻¹ at 323 K. Experimental data were evaluated using adsorption isotherm models, kinetic studies, and thermodynamic analyses. Temkin model was provided the best fit to the experimental data among the applied four isotherm models (Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin). Adsorption kinetics were evaluated with three models and adsorption process was followed the PSO kinetic model most accurately, which has the highest R² values. Thermodynamic analysis for adsorption of 120 mg L⁻¹ initial MB concentration at 323 K was revealed negative values for Gibbs free energy (-3483.06 J mol⁻¹), along with positive enthalpy values (22342.73 J mol⁻¹) and entropy (79.95 J mol⁻¹K⁻¹). These results were showed that adsorption process was spontaneous and endothermic in nature and the activation energy was calculated to be 13.97 kJ mol⁻¹. These findings were suggested that prepared PSA adsorbent represents a promising low-cost alternative to conventional adsorbents for effective removal of dye pollutants from wastewater.

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References

[1]. E. Daneshvar, A. Vazirzadeh, A. Niazi, M. Kousha, M. Naushad, A. Bhatnagar, ‘‘Desorption of methylene blue dye from brown macroalga: effects of operating parameters, isotherm study and kinetic modeling.’’ Journal of Cleaner Production, vol. 152, pp. 443–453, 2017. https://doi.org/10.1016/j.jclepro.2017.03.119.

[2]. T. K. Das, S. K. Ghosh, N. C. Das, ‘‘Green synthesis of a reduced graphene oxide/silver nanoparticles-based catalyst for degradation of a wide range of organic pollutants.’’ Nano-Structures & Nano-Objects, vol. 34, pp. 100960, 2023. http://dx.doi.org/10.2139/ssrn.4224529

[3]. N. Mladenov, N. G. Dodger, L. Steinberg, W. Richardot, J. Johnson, B. S. Martincigh, C. Buckley, T. Lawrence, E. Hoh, ‘‘Persistence and removal of trace organic compounds in centralized and decentralized wastewater treatment systems.’’ Chemosphere, vol. 286, pp. 131621, 2022. https://doi.org/10.1016/j.chemosphere.2021.131621

[4]. U. O. Aigbe, K. E. Ukhurebor, R. B. Onyancha, O. A. Osibote, H. Darmokoesoemo, H. S. Kusuma, ‘‘Fly ash-based adsorbent for adsorption of heavy metals and dyes from aqueous solution: a review.’’ Journal of Material Research Technology, vol. 14, pp. 2751–2774, 2021. https://doi.org/10.1016/j.jmrt.2021.07.140

[5]. D. S. Tong, C. W. Wu, M. O. Adebajo, G. C. Jin, W. H. Yu, S. F. Ji, C. H. Zhou, (2018). ‘‘Adsorption of methylene blue from aqueous solution onto porous cellulose-derived carbon/montmorillonite nanocomposites.’’ Applied Clay Science, vol. 161, pp. 256-264, 2018. https://doi.org/10.1016/j.clay.2018.02.017

[6]. E. Alver, A. Ü. Metin, F. Brouers, ‘‘Methylene blue adsorption on magnetic alginate/rice husk bio-composite.’’ International Journal of Biological Macromolecules, vol. 154, pp. 104-113, 2020. https://doi.org/10.1016/j.ijbiomac.2020.02.330

[7]. R. L. Singh, P. K. Singh, R. P. Singh, ‘‘Enzymatic decolorization and degradation of azo dyes – a review.’’ International Biodeterioration & Biodegradation, vol. 104, pp. 21–31, 2015. https://doi.org/10.1016/j.ibiod.2015.04.027

[8]. A. A. Spagnoli, D. A. Giannakoudakis, S. Bashkova, ‘‘Adsorption of methylene blue on cashew nut shell based carbons activated with zinc chloride: the role of surface and structural parameters.’’ Journal of Molecular Liquids, vol. 229, pp. 465–471, 2017. https://doi.org/10.1016/j.molliq.2016.12.106

[9]. F. Dhaouadi, L. Sellaoui, G. L. Dotto, A. Bonilla-Petriciolet, A. Erto, A. B. Lamine, ‘‘Adsorption of methylene blue on comminuted raw avocado seeds: Interpretation of the effect of salts via physical monolayer model.’’ Journal of Molecular Liquids, vol. 305, pp. 1-8, 2020. https://doi.org/10.1016/j.molliq.2020.112815

[10]. Y. Liu, Y. Liu, R. Qu, C. Ji, C. Sun, ‘‘Comparison of adsorption properties for anionic dye by metal organic frameworks with different metal ions.’’ Colloids and Surfaces A: Physicochemical and Engineering Aspects, vol. 586, pp. 1-7, 2020. https://doi.org/10.1016/j.colsurfa.2019.124259

[11]. M. F. Chowdhury, C. M. Kim, A. Jang, ‘‘High-efficient and rapid removal of anionic and cationic dyes using a facile synthesized sole adsorbent NiAlFe-layered triple hydroxide (LTH).’’ Chemosphere, vol. 332, pp. 138878, 2023. https://doi.org/10.1016/j.chemosphere.2023.138878

[12]. Y.-G. Kang, H. Yoon, C.-S. Lee, E.-J. Kim, Y.-S. Chang, ‘‘Advanced oxidation and adsorptive bubble separation of dyes using MnO2-coated Fe3O4 nanocomposite.’’ Water Research, vol. 151, pp. 413-422, 2019. https://doi.org/10.1016/j.watres.2018.12.038

[13]. A. Muniyasamy, G. Sivaporul, A. Gopinath, R. Lakshmanan, A. Altaee, A. Achary, P. V. Chellam, ‘‘Process development for the degradation of textile azo dyes (mono-, di-, poly-) by advanced oxidation process - ozonation: experimental & partial derivative modelling approach.’’ Journal of Environmental Management, vol. 265, pp. 1-10, 2020. https://doi.org/10.1016/j.jenvman.2020.110397

[14]. P. Zhang, B. Liu, T. Zhao, J. Yu, X. Ye, X. Chen, ‘‘Degradation of typical nitrogen‑heterocyclic compounds in coal gasification wastewater via catalytic ozonation processes.’’ Water Air Soil Pollution, vol. 235(793), pp. 1–11, 2024. https://doi.org/10.1007/s11270-024-07516-4

[15]. M. A. Alsaffar, M. A. Rahman, A. K. Mageed, S. A. K. Ali, T. Lutfee, S. W. Adnan, H. A. A. Shakir, ‘‘Electrochemical removal of dye from a tanning process industrial wastewater.’’ Chemical Papers, vol. 77, pp. 6311–6318, 2023. https://doi.org/10.1007/s11696-023-02940-y

[16]. L. A., Pereira, A. B., Couto, D. A. L., Almeida, N. G. Ferreira, ‘‘Singular properties of boron-doped diamond/carbon fiber composite as anode in Brilliant Green dye electrochemical degradation.’’ Diamond and Related Materials, vol. 103, pp. 1-7, 2020. https://doi.org/10.1016/j.diamond.2020.107708

[17]. J. Joseph, R. C. Radhakrishnan, J. K. Johnson, S. P. Joy, J. Thomas, ‘‘Ion-exchange mediated removal of cationic dye-stuffs from water using ammonium phosphomolybdate.’’ Materials Chemistry and Physics, vol. 242, pp. 1-8, 2020. https://doi.org/10.1016/j.matchemphys.2019.122488

[18]. N. N. Ayhan, A. Aldemir, & A. Özgüven, ‘‘Treatment of petroleum refinery wastewater by chemical coagulation method: determination of optimum removal conditions using experimental design.’’ Brazilian Journal of Chemical Engineering, vol. 41, pp. 121-137, 2024. https://doi.org/10.1007/s43153-023-00358-3

[19]. A. Aldemir, E. Hakkıtanır, A. Özgüven, ‘‘Determination of optimum treatment conditions for paint industry wastewater with the coagulation/flocculation method.’’ Desalination & Water Treatment, vol. 211, pp. 165–176, 2021. https://doi.org/10.5004/dwt.2021.26624

[20]. A. Aldemir, A. Turan, A. R. Kul, H. Koyuncu, ‘‘Comprehensive investigation of Basic Red 46 removal by pinecone adsorbent: experimental, isotherm, kinetic and thermodynamic studies.’’ International Journal of Environmental Science & Technology, vol. 383, no.1 pp.1-26, 2023. https://doi.org/10.1007/s13762-022-04456-6

[21]. A. R. Kul, H. Koyuncu, A. Turan, A. Aldemir, ‘‘Comparative research of isotherm, kinetic and thermodynamic studies for neutral red adsorption by activated carbon prepared from apple peel.’’ Water Air Soil Pollution, vol. 383, pp. 1-26, 2023. https://doi.org/10.1007/s11270-023-06392-8

[22]. M. A. M. Salleh, D. K. Mahmoud, W. A. W. A. Karim, A. Idris, ‘‘Cationic and anionic dye adsorption by agricultural solid wastes: a comprehensive review.’’ Desalination, vol. 280, no. (1-3), pp. 1–13, 2011. https://doi.org/10.1016/j.desal.2011.07.019

[23]. M. T. Yagub, T. K. Sen, S. Afroze, H. M. Ang, ‘‘Dye and its removal from aqueous solution by adsorption: a review.’’ Advances Colloid and Interface Science, vol. 209, pp. 172–184, 2014. https://doi.org/10.1016/j.cis.2014.04.002

[24]. V. Katheresan, J. Kansedo, S. Y. Lau, ‘‘Efficiency of various recent wastewater dye removal methods: A review.’’ Journal of Environmental Chemical Engineering, vol. 6 no. 1, pp. 4676–4697, 2018. https://doi.org/10.1016/j.jece.2018.06.060

[25]. M. A., Ahmad, N. Ahmad, & O. S. Bello, ‘‘Modified durian seed as adsorbent for the removal of methyl red dye from aqueous solutions.’’ Applied Water Science, vol. 5, pp. 407–423, 2015. https://doi.org/10.1007/s13201-014-0208-4

[26]. G. V. Demirci, M. T. Baig, A. Kayan, ‘‘UiO-66 MOF/Zr-di-terephthalate/cellulose hybrid composite synthesized via sol-gel approach for the efficient removal of methylene blue dye.’’ International Journal of Biological Macromolecules, vol. 283, pp. 1–16, 2024. https://doi.org/10.1016/j.ijbiomac.2024.137950

[27]. H. N. Bhatti, Y. Safa, S. M. Yakout, O. H. Shair, M. Iqbal, A. Nazir, ‘‘Efficient removal of dyes using carboxymethyl cellulose/alginate/polyvinyl alcohol/rice husk composite: Adsorption/desorption, kinetics and recycling studies.’’ International Journal of Biological Macromolecules, vol. 150, pp. 861-870, 2020. https://doi.org/10.1016/j.ijbiomac.2020.02.093

[28]. S. B. Dutta, B. Gupta, S. K. Srivastava, & A. K. Gupta, ‘‘Recent advances on the removal of dyes from wastewater using various adsorbents: A critical review.’’ Materials Advances, vol. 2, no. 14, pp. 4497–4531, 2021. https://doi.org/10.1039/d1ma00354b

[29]. H. Zeghioud, L. Fryda, A. Mahieu, R. Visser, A. Kane, ‘‘Potential of flax shives and beech wood-derived biochar in methylene blue and carbamazepine removal from aqueous solutions.’’ Materials, vol. 15, pp. 2824, 2022b. https://doi.org/10.3390/ma15082824

[30]. M. Rafatullah, O. Sulaiman, R. Hashim, A. Ahmad, ‘‘Adsorption of methylene blue on low-cost adsorbents: a review.’’ Journal of Hazardous Materials, vol. 177, no. 1–3, pp. 70–80, 2010. https://doi.org/10.1016/j.jhazmat.2009.12.047

[31]. A. H. Jawad, R. Razuan, J. N. Appaturi, L. D. Wilson, ‘‘Adsorption and mechanism study for methylene blue dye removal with carbonized watermelon (Citrullus lanatus) rind prepared via one-step liquid phase H2SO4 activation.’’ Surfaces and Interfaces, vol. 16, pp. 76-84, 2019. https://doi.org/10.1016/j.surfin.2019.04.012

[32]. I. Khan, K. Saeed, I. Zekker, B. Zhang, A. H. Hendi, A. Ahmad, S. Ahmad, N. Zada, H. Ahmad, L. A. Shah, T. Shah, I. Khan, ‘‘Review on methylene blue: its properties, uses, toxicity and photodegradation.’’ Water, vol. 14, pp. 242–271, 2022. https://doi.org/10.3390/w14020242

[33]. S. J. Peighambardoust, D. C. Boffito, R. Foroutan, B. Ramavandi, B, ‘‘Sonophotocatalytic activity of sea sediment@400/ZnO catalyst to remove cationic dyes from wastewater.’’ Journal of Molecular Liquids, vol. 367, pp. 120478, 2022. https://doi.org/10.1016/j.molliq.2022.120478

[34]. P.O. Oladoye, T. O. Ajiboye, E. O. Omotola, O. J. Oyewola, ‘‘Methylene blue dye: toxicity and potential elimination technology from wastewater.’’ Results in Engineering, vol. 16, pp. 1–17, 2022. https://doi.org/10.1016/j.rineng.2022.100678

[35]. E. Misran, M. D. Supardan, D. A. Iryani, V. Pramananda, A. F. Sihombing, D. V. Sitorus, ‘‘Ultrasonic assisted adsorption of methylene blue using blood clam shell as a low-cost adsorbent.’’ Results in Engineering, vol. 23, pp. 1–13, 2024. https://doi.org/10.1016/j.rineng.2024.102715

[36]. S. Parlayıcı, A. Aras, ‘‘Synthesis of a novel green biopolymer-based composites beads for removal of methylene blue from aquatic medium: isotherm, thermodynamic and kinetic investigation.’’ Polymer Bulletin, vol. 81, no. 7, pp. 6603–6640, 2024. https://doi.org/10.1007/s00289-024-05164-6

[37]. A. R. Kul, A. Aldemir, ‘‘An investigation of aniline removal performance by the activated carbon prepared from biomass conversion: adsorption results of isotherm, kinetic and thermodynamic studies.’’ Biomass Conversion & Biorefinery, vol. 15, pp. 19915-19930, 2025. https://doi.org/10.1007/s13399-024-06433-0

[38]. S. Lagergren, B. K. Svenska, ‘‘Zur theorie der sogenannten adsorption geloester stoffe,’’ Veternskapsakad Handlingar, vol 24, pp. 1-39, 1898.

[39]. Y. S. Ho, G. Mckay, ‘‘Kinetic models for the sorption of dye from aqueous solution by wood.’’ Process Safety and Environmental Protection, vol. 76, pp. 183-191, 1998.

[40]. W. J. Weber, J. C. Morris, ‘‘Kinetics of adsorption on carbon from solution.’’ Journal of the Sanitary Engineering Division, vol. 89, pp. 31-60, 1963.

[41]. J. Wang, X. Guo, ‘‘Adsorption isotherm models: classification, physical meaning, application and solving method.’’ Chemosphere, vol. 258, pp. 127279, 2020. https://doi.org/10.1016/j.chemosphere.2020.127279

[42]. T. Santhi, S. Manonmani, T. Smitha, ‘‘Kinetics and isotherm studies on cationic dyes adsorption onto Annona Squmosa seed activated carbon.’’ International Journal of Engineering Science & Technology, vol. 2, pp. 287–295, 2010.

[43]. X. Guo, W. H. Briscoe, ‘‘Molecular interactions, elastic properties, and nanostructure of Langmuir bacterial-lipid monolayers: towards solving the mystery in bacterial membrane asymmetry.’’ Current Opinion Colloid Interface Science, vol. 67, pp. 101731, 2023. https://doi.org/10.1016/j.cocis.2023.101731.

[44]. A. Yar, S. Parlayici, ‘‘Carbon nanotubes/polyacrylonitrile composite nanofiber mats for highly efficient dye adsorption.’’ Colloids Surf. A Physicochemical Engineering Asp. vol. 651, pp. 129703, 2022. https://doi.org/10.1016/j.colsurfa.2022.129703

[45]. S. Kalam, S. A. Abu-Khamsin, M. S. Kamal, S. Patil, ‘‘Surfactant adsorption isotherms: a review.’’ ACS Omega, vol. 6, no. 48, pp. 32342–32348, 2021. https://doi.org/10.1021/ACSOMEGA.1C04661/ASSET/ IMAGES/MEDIUM/AO1C04661_M047.GIF.

[46]. O. Baytar, A. A. Ceyhan, O. Şahin, ‘‘Production of activated carbon from Elaeagnus angustifolia seeds using H3PO4 activator and methylene blue and malachite green adsorption.’’ International Journal of Phytoremediation, vol. 23, no. 7, pp. 693–703, 2021. https://doi.org/10.1080/15226514.2020.1849015

[47]. A. H. Jawad, A. S. Abdulhameed, M. S. Mastuli, ‘‘Acid-factionalized biomass material for methylene blue dye removal: a comprehensive adsorption and mechanism study.’’ Journal of Taibah University Science, vol. 14, no. 1, pp. 305–313, 2020a. https://doi.org/10.1080/16583655.2020.1736767

[48]. H. Shi, W. Li, L. Zhong, C. Xu, ‘‘Methylene blue adsorption from aqueous solution by magnetic cellulose/graphene oxide composite: equilibrium, kinetics, and thermodynamics.’’ Industrial Engineering Chemistry Research, vol. 53, pp. 1108–1118, 2014. https://doi.org/10.1021/ie4027154

[49]. L. Mouni, L. Belkhiri, J.-C., Bollinger, A. Bouzaza, A. Assadi, A. Tirri, F. Dahmoune, K. Madani, H. Remini, ‘‘Removal of Methylene Blue from aqueous solutions by adsorption on Kaolin: kinetic and equilibrium studies.’’ Applied Clay Science, vol. 153, pp. 38–45, 2018. https://doi.org/10.1016/j.clay.2017.11.034

[50]. H. A. Al-Husseiny, ‘‘Adsorption of methylene blue dye using low cost adsorbent of sawdust: batch and continues studies.’’ Journal of University of Babylon, vol. 22, no. 2, pp. 296-310, 2014.

[51]. G. I. Supelano, J. A. G´omez Cuaspud, L. C. Moreno-Aldana, C. Ortiz, C. A., Trujillo, C. A., Palacio, C. A. Parra Vargas, J. A. Mejía G´omez, ‘‘Synthesis of magnetic zeolites from recycled fly ash for adsorption of methylene blue.’’ Fuel, vol. 263, pp. 116800, 2020. https://doi.org/10.1016/j.fuel.2019.116800

[52]. L. Lonappan, T. Rouissi, R. K. Das, S. K. Brar, A. A. Ramirez, M. Verma, R. Y. Surampalli, J. R. Valero, ‘‘Adsorption of methylene blue on biochar microparticles derived from different waste materials.’’ Waste Management, vol. 49, pp. 537–544, 2016. https://doi.org/10.1016/j.wasman.2016.01.015

[53]. P. Staro´n, J. Chwastowski, M. Banach, ‘‘Sorption behaviour of methylene blue from aqueous solution by raphia fibers.’’ International Journal of Environmental Science & Technology, vol. 16, pp. 8449–8460, 2019. https://doi.org/10.1007/s13762-019-02446-9

[54]. X. L. Ren, X. Q. Shu, W. G. Geng, P. Li, Y. E. Xu, ‘‘A study on the adsorption of methylene blue by acid-modified coal measures kaolin.’’ Processes, vol. 12, pp. 773, 2024. https://doi.org/10.3390/pr12040773

[55]. J. X. Wang, Y. F. Tan, H. J. Yang, L. L. Zhan, G. W. Sun, L. Luo, ‘‘On the adsorption characteristics and mechanism of methylene blue by ball mill modified biochar.’’ Scientific Reports, vol. 13, pp. 21174, 2023. https://doi.org/10.1038/s41598-023-48373-1

[56]. M. T. Uddin, M. A., Islam, S. Mahmud, M. Rukanuzzaman, ‘‘Adsorptive removal of methylene blue by tea waste.’’Journal of Hazardous Materials, vol. 164, pp. 53–60, 2009. https://doi.org/10.1016/j.jhazmat.2008.07.131

[57]. B. S. Inbaraj, K. Selvarani, N. Sulochana, ‘‘Evaluation of a carbonaceous sorbent prepared from pearl millet husk for its removal of basic dyes.’’ Journal of Scientific Industrial Research, vol. 61, pp. 971–978, 2002.

[58]. C. B. Godiya, L. A. M. Ruotolo, ‘‘Plant leaves waste for removal of metal ions.’’ Emerging Techniques for Treatment Toxic Metals from Wastewater, pp. 47–82, 2023.https://doi.org/10.1016/B978-0-12-822880-7.00014-5

[59]. Momina, S. Mohammad, I. Suzylawati, ‘‘Study of the adsorption/desorption of MB dye solution using bentonite adsorbent coating.’’ Journal of Water Process Engineering, vol. 34, pp. 101155, 2020. https://doi.org/10.1016/j.jwpe.2020.101155

[60]. M. J. Ahmed, P. U. Okoye, E. H. Hummadi, B. H. Hameed, ‘‘High-performance porous biochar from the pyrolysis of natural and renewable seaweed (Gelidiella acerosa) and its application for the adsorption of methylene blue.’’ Bioresource Technology, vol. 278, pp. 159-164, 2019. https://doi.org/10.1016/j.biortech.2019.01.054

[61]. A. K. Cordova Estrada, F. Lozano, Cordova, R. A. Lara Díaz, ‘‘Thermodynamics and kinetic studies for the adsorption process of methyl orange by magnetic activated carbons.’’ Air Soil Water Research, vol. 14, pp. 1-11, 2021. https://doi.org/10.1177/11786221211013336/

An Evaluation for Adsorption Behaviour and Mechanism of Methylene Blue on Peach Seeds: Isotherm, Kinetic and Thermodynamic Studies