Adsorption behavior and mechanism of malachite green dye onto natural bentonite from Sa Bot district, Lopburi province, Thailand
Article Sidebar
Main Article Content
Abstract
Dye-laden wastewater poses a persistent environmental challenge due to its toxicity and resistance to degradation. This study reports the novel application of natural bentonite sourced from Sa Bot district, Lopburi province, Thailand, for the adsorption of cationic malachite green (MG) dye. The distinct geological origin of this bentonite, which has not been previously investigated for MG dye removal, underscores its unique physicochemical properties and local relevance. Comprehensive characterization was performed using BET surface area analysis, FTIR spectroscopy, SEM-EDXS, and determination of the point of zero charge (pHpzc). Batch adsorption experiments systematically examined the effects of pH, adsorbent dose, contact time, initial dye concentration, and temperature. Optimal adsorption occurred at pH 9, with equilibrium being reached within 180 minutes, yielding a maximum adsorption capacity of 35.97mg/g at 30°C. Equilibrium data were well fitted to both Langmuir and Freundlich models, while the Redlich–Peterson model indicated surface heterogeneity. Kinetic analysis confirmed pseudo-second-order behavior, with intraparticle diffusion contributing alongside surface adsorption. Thermodynamic evaluation revealed that the process was endothermic and spontaneous across 20-40°C, as evidenced by negative ∆G values throughout this temperature range. Mechanistic insights highlighted electrostatic interactions, hydrogen bonding, n–π interactions, pore filling, and ion exchange. Furthermore, the bentonite demonstrated excellent reusability, maintaining stable performance over five regeneration cycles. These findings establish locally sourced bentonite as a cost-effective, sustainable adsorbent with practical significance for industrial wastewater treatment.
Article Details
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
Published manuscript are the rights of their original owners and RMUTSB Academic Journal. The manuscript content belongs to the authors' idea, it is not the opinion of the journal's committee and not the responsibility of Rajamangala University of Technology Suvarnabhumi
References
Abbas, M., & Trari, M. (2020). Removal of methylene blue in aqueous solution by economic adsorbent derived from apricot stone activated carbon. Fibers and Polymers, 21, 810-820. https://doi.org/10.1007/s12221-020-8630-8
Abbas, M., & Trari, M. (2023). Contribution of zeolite to remove malachite green in aqueous solution by adsorption processes: Kinetics, isotherms and thermodynamic studies. Textile Research Journal, 93(15-16), 3765-3776. https://doi.org/10.1177/00405175231165336
Abewaa, M., Mengistu, A., Takele, T., Fito, J., & Nkambule, T. (2023). Adsorptive removal of malachite green dye from aqueous solution using Rumex abyssinicus-derived activated carbon. Scientific Reports, 13(1), 14701. https://doi.org/10.1038/s41598-023-41957-x
Aggarwal, P., Umar, F., & Paul, A. (2025). Review of ordered pores in nanomaterials for energy applications ranging from energy storage to catalysis. ACS Applied Nano Material, 8, 17780-17818. https://doi.org/10.1021/acsanm.5c03047
Alexander, J. A., Ahmad Zaini, M. A., Surajudeen, A., Aliyu, E. N. U., & Omeiza, A. U. (2019). Surface modification of low-cost bentonite adsorbents: A review. Particulate Science and Technology, 37(5), 538-549. https://doi.org/10.1080/02726351.2018.1438548
Almeida, C. A. P., Debacher, N. A., Downs, A. I., Cottet, L., & Mello, C. A. D. (2009). Removal of methylene blue from colored effluents by adsorption on monmorillonite clay. Journal of Colloid and Interface Science, 332(1), 46-53. https://doi.org/10.1016/j.jcis.2008.12.012
Baidya, K. S., & Kumar, U. (2021). Adsorption of brilliant green dye from aqueous solution onto chemically modified areca nut husk. South African Journal of Chemical Engineering, 35, 33-43. https://doi.org/10.1016/j.sajce.2020.11.001
Bhat, S. S., Narayana, B., & Bhat, J. I. (2023). Adsorption of malachite green dye using low-cost adsorbent derived from java apple leaves (syzyium samarangense). Sādhanā, 48(3), 138. https://doi.org/10.1007/s12046-023-02214-z
Belkhodja, A., Choukchou-Braham, E., Benkhaled, A., Guendouz, S., & Attar, T. (2026). Study of the adsorption of a textile dye by alginate-bentonite beads: CCD-RSM design conception. Journal of Macromolecular Science Part B, 65(4), 567-589. https://doi.org/10.1080/00222348.2024.2437854
Bergaoui, M., Nakhli, A., Yeo, J. Y. J., Soetaredjo, F. E., Ismadji, S., Sunarso, J., & Khalfaoui, M. (2023). Novel insights on the adsorption ability of bentonite and its chitosan composite: Deep understanding of antibiotics removal as hazardous agents. Journal of Molecular Liquids, 387, 122550. https://doi.org/10.1016/j.molliq.2023.122550
Borah, D., Nath, H., & Saikia, H. (2022). Purification of crude bentonite clay: Synthesis and characterization of Na, Mg and Cu incorporated bentonite clay. Asian Journal of Chemistry, 34(5), 1237-1244. https://doi.org/10.14233/ajchem.2022.23697
Boumad, S., Cano-Casanova, L., Román-Martínez, M. C., Bouchenafa-Saib, N., & Lillo-Rodenas, M. A. (2024). Removal of malachite green from water: Comparison of adsorption in a residue-derived AC versus photocatalytic oxidation with TiO2 and study of the adsorption-photocatalysis synergy. Environmental Research, 250, 118510. https://doi.org/10.1016/j.envres.2024.118510
Bullen, J. C., Saleesongsom, S., Gallagher, K., Dominik, J., & Weiss, D. J. (2021). A revised pseudo-second-order kinetic model for adsorption, sensitive to changes in adsorbate and adsorbent concentrations. Langmuir, 37(10), 3189-3201. https://doi.org/10.1021/acs.langmuir.1c00142
Cheng, S., Zhang, L., Xia, H., Peng, J., Shu, J., Li, C., Jiang, X., & Zhang, Q. (2017). Adsorption behavior of methylene blue on waste-derived adsorbent and exhaust gases recycling. RSC Advances, 7, 27331. https://doi.org/10.1039/c7ra01482a
Cui, Q., Huang, Y., Ma, X., Li, S., Bai, R., Li, H., Liu, W., & Wei, H. (2024). Research on the adsorption mechanism and performance of cotton stalk-based biochar. Molecules, 29, 5841. https://doi.org/10.3390/molecules29245841
Djelloul, C., Hasseine, A., & Hamdaouic, O. (2017). Adsorption of cationic dye from aqueous solution by milk thistle seeds: Isotherm, kinetic and thermodynamic studies. Desalination and Water Treatment, 78, 313-320. https://doi.org/10.5004/dwt.2017.20920
Doke, K. M., & Khan, E. M. (2012). Equilibrium, kinetic, and diffusion mechanism of Cr (VI) adsorption onto activated carbon derived from wood apple shell. Arabian Journal of Chemistry, 10, S252-S260. https://doi.org/10.1016/j.arabjc.2012.07.031
Dutta, S., Gupta, B., Srivastava, S. K., & Gupta, A. K. (2021). Recent advances on the removal of dyes from wastewater using various adsorbents: A critical review. Materials Advances, 2(14), 4497-7311. https://doi.org/10.1039/d1ma00354b
El Haddad, M. (2016). Removal of basic fuchsin dye from water using mussel shell biomass waste as an adsorbent: Equilibrium, kinetics, and thermodynamics. Journal of Taibah University for Science, 10(5), 664-674. https://doi.org/10.1016/j.jtusci.2015.08.007
Fernandes, J. V., Rodrigues, A. M., Menezes, R. R., & Neves, G. D. A. (2020). Adsorption of anionic dye on the acid-functionalized bentonite. Materials, 13(16), 3600. https://doi.org/10.3390/ma13163600
Gandhi, D., Bandyopadhyay, R., & Soni, B. (2022). Naturally occurring bentonite clay: Structural augmentation, characterization and application as catalyst. Material Today: Proceedings, 57(1), 194-201. https://doi.org/10.1016/j.matpr.2022.02.346
Gebreslassie, Y. T. (2020). Equilibrium, kinetics, and thermodynamic studies of malachite green adsorption onto fig (Ficus cartia) leaves. Journal of Analytical Methods in Chemistry, 2020(1), 7384675. https://doi.org/10.1155/2020/7384675
Hakim, Y. M., Mohadi, R., Mardiyanto., & Royani, I. (2023). Ammonium-assisted intercalation of Java bentonite as effective of cationic dye removal. Journal of Ecological Engineering, 24(2), 184-195. https://doi.org/10.12911/22998993/156665
Hamad, H. N., Idrus, S., Yusuf, B., Jamali, N. S., Ahsan, A., Suhartini, S., & Wahab, A. M. A. (2024). Optimized bentonite clay adsorbents for methylene blue removal. Processes, 12(4), 738. https://doi.org/10.3390/pr12040738
Hasani, N., Selimi, T., Mele, A., Thaci, V., Halili, J., Berisha, A., & Sadiku, M. (2022). Theoretical, equilibrium, kinetics and thermodynamic investigations of methylene blue adsorption onto lignite coal. Molecules, 27, 1856. https://doi.org/10.3390/molecules27061856
Huang, Z., Li, Y., Chen, W., Shi, J., Zhang, N., Wang, X., Li, Z., Gao, L., & Zhang, Y. (2017). Modified bentonite adsorption of organic pollutants of dye wastewater. Materials Chemistry and Physics, 202, 266-276. https://doi.org/10.1016/j.matchemphys.2017.09.028
Kalam, S., Abu-Khamsin, S., Kamal, M. S., & Patil, S. (2021). Surfactant adsorption isotherms: Review. ACS Omega, 6(48), 32342-32348. https://doi.org/10.1021/acsomega.1c04661
Kathing, C., & Saini, G. (2022). A review of various treatment methods for the removal of dyes from textile effluent. Recent Progress in Materials, 4(4), 028. https://doi.org/10.21926/rpm.2204028
Keereerak, A., & Chinpa, W. (2020). A potential biosorbent from Moringa oleifera pod husk for crystal violet adsorption: Kinetics, isotherms, thermodynamic and desorption studies. ScienceAsia, 46(2), 186-194. https://doi.org/10.2306/scienceasia1513-1874.034
Kumar, P. S. (2013). Adsorption of Zn (II) ions from aqueous environment by surface modified strychnos potatorum seeds, a low-cost adsorbent. Polish Journal of Chemical Technology, 15(3), 35-41. https://doi.org/10.2478/pjct-2013-0041
Kurniawan, A., Sutiono, H., Indraswati, N., & Ismadji, S. (2012). Removal of basic dyes in binary system by adsorption using rarasaponin–bentonite: Revisited of extended Langmuir model. Chemical Engineering Journal, 189-190, 264-274. https://doi.org/10.1016/j.cej.2012.02.070
Kusumlata, Ambade, B., Kumar, A., & Gautam, S. (2024). Sustainable solutions: Reviewing the future of textile dye contaminant removal with emerging biological treatments. Limnological Review, 24(2), 126-149. https://doi.org/10.3390/limnolrev24020007
Lafi, R., Montasser, I., & Hafiane, A. (2019). Adsorption of congo red dye from aqueous solutions by prepared activated carbon with oxygen-containing functional groups and its regeneration. Adsorption Science & Technology, 37(1-2), 160-181. https://doi.org/10.1177/0263617418819227
Li, X., Wen, B., & Li, Y. (2020). Adsorption of the malachite green by magnetic clam shell powder. Polish Journal of Environmental Studies, 30(1), 717-726. https://doi.org/10.15244/pjoes/123826
Liang, C., Shi, Q., Feng, J., Yao, J., Huang, H., & Xie, X. (2022). Adsorption behaviors of cationic methylene blue and anionic reactive blue 19 dyes onto nano-carbon adsorbent carbonized from small precursors. Nanomaterials, 12, 1814. https://doi.org/10.3390/nano12111814
Lucaci, A. R., & Bulgariu, L. (2024). Biosorption of technologically valuable metal ions on algae wastes: Laboratory studies and applicability. Water, 16(4), 512. https://doi.org/10.3390/w16040512
Ma, J., Ma, Q., Wang, Q., Li, Y., Ji, W., Ma, Y., Sun, Y., & Li, Y. (2026). Synergistic enhancement of Pb2+ adsorption by hierarchical pore structure and ultralow Si/Al ratio in bentonite-derived sodalite. ACS Applied Materials & Interfaces, 18(6), 10521-10538. https://doi.org/10.1021/acsami.5c20799
Mansour, R., Simeda, G., & Zaatout, A. (2020). Adsorption studies on brilliant green dye in aqueous solutions using activated carbon derived from guava seeds by chemical activation with phosphoric acid. Desalination and Water Treatment, 202, 396-409. https://doi.org/10.5004/dwt.2020.26147
Mahinroosta, M., Moattari, R. M., Allahverdi, A., & Ghadir, P. (2024). Malachite green dye removal with aluminosilicate nanopowder from aluminum dross and silicomanganese slag. Circular Economy, 3, 100100. https://doi.org/10.1016/j.cec.2024.100100
Mahmoud, A. S. (2022). Effect of nano bentonite on direct yellow 50 dye removal: Adsorption isotherm, kinetic analysis, and thermodynamic behavior. Progress in Reaction Kinetics and Mechanism, 47, 1-23. https://doi.org/10.1177/14686783221090377
Maimulyanti, A., Prihadi, A. R., Rosita, T., & Safrudin, I. (2019). Adsorption and recovery of aroma compounds from wastewater of clove oil distillation using coffee husk biosorbent. ScienceAsia, 45(5), 446. https://doi.org/10.2306/scienceasia1513-1874.2019.45.446
Mecheri, R., Zobeidi, A., Atia, S., Nacer, S. N., Salih, A. A. M., Benaissa, M., Ghernaout, D., Arni, S. A, Ghareba, S., & Elboughdiri, N. (2023). Modeling and optimizing the crystal violet dye adsorption on kaolinite mixed with cellulose waste red bean peels: Insights into the kinetic, isothermal, thermodynamic, and mechanistic study. Materials, 16, 4082. https://doi.org/10.3390/ma16114082
Messaoudi, M., Douma, M., Tijani, N., Dehmani, Y., & Messaoudi, L. (2021). Adsorption process of the malachite green onto clay: Kinetic and thermodynamic studies. Desalination and Water Treatment, 240, 191-202. https://doi.org/10.5004/dwt.2021.27688
Momina, Mohammada, S., & Isamila, S. (2020). Study of the adsorption/desorption of MB dye solution using bentonite adsorbent coating. Journal of Water Process Engineering, 34, 101155. https://doi.org/10.1016/j.jwpe.2020.101155
Nirmaladevi, S., & Palanisamy, N. (2020). A comparative study of the removal of cationic and anionic dyes from aqueous solutions using biochar as an adsorbent. Desalination and Water Treatment, 175, 282-292. https://doi.org/10.5004/dwt.2020.24906
Pawar, R. P., Lalhmunsiama, Bajaj, H. C., & Lee, S. M. (2016). Activated bentonite as a low-cost adsorbent for the removal of Cu(II) and Pb(II) from aqueous solutions: Batch and column studies. Journal of Industrial and Engineering Chemistry, 34, 213-223. https://doi.org/10.1016/j.jiec.2015.11.014
Piriya, R. S., Jayabalakrishnan, R. M., Maheswari, M., Boomiraj, K., & Oumabady, S. (2023). Comparative adsorption study of malachite green dye on acid-activated carbon. International Journal of Environmental Analytical Chemistry, 103(1), 16-30. https://doi.org/10.1080/03067319.2020.1849667
Queiroga, L. N. F., Pereira, M. B. B., Silva, L. S., Filho, E. C. S., Santos, I. M. G., Fonseca, M. G., Thomas Georgelinc, T., & Jaberd, M. (2019). Microwave bentonite silylation for dye removal: Influence of the solvent. Applied Clay Science, 168, 478-487. https://doi.org/10.1016/j.clay.2018.11.027
Ramu, A. G., & Choi, D. (2021). Highly efficient and simultaneous catalytic reduction of multiple toxic dyes and nitrophenols waste water using highly active bimetallic PdO–NiO nanocomposite. Scientific Reports, 11(1), 22699. https://doi.org/10.1038/s41598-021-01989-7
Sartape, A. S., Mandhare, A. M., Jadhav, V. V., Raut, P. D., Anuse, M. A., & Kolekar, S. S. (2017). Removal of malachite green dye from aqueous solution with adsorption technique using Limonia acidissima (wood apple) shell as low cost adsorbent. Arabian Journal of Chemistry, 10, S3229-S3238. https://doi.org/10.1016/j.arabjc.2013.12.019
Sawasdee, S., Chakerd, H., Pannasiri, W., & Watcharabundit, P. (2018). The COD removal in chemical laboratory wastewater by using sugarcane bagasse-activated carbon. RMUTSB Academic Journal, 6(1), 55-64. https://li01.tci-thaijo.org/index.php/rmutsb-sci/article/view/124253
Sehar, S., Rasool, T., Syed, H. M., Mir, M. A., Naz, I., Rehman, A., Shah, M. S., Akhter, M. S., Mahmood, Q., & Younis, A. (2022). Recent advances in biodecolorization and biodegradation of environmentally threatening textile finishing dyes. 3 Biotech, 12(8), 186. https://doi.org/10.1007/s13205-022-03247-7
Söğüt, E. G., Ergan, E., Kılıç, N. C., Dönmez. H., & Akbaş, E. (2021). Methylene blue adsorption from aqueous solution by functionalized perlites: An experimental and computational chemistry study. Desalination and Water Treatment, 217, 391-410. https://doi.org/10.5004/dwt.2021.26752
Taibi, Z., Bentaleb, K., Bouberka, Z., Pierlot, C., Vandewalle, M., Volkringer, C., Supiot, P., & Maschke, U. (2023). Adsorption of orange G dye on hydrophobic activated bentonite from aqueous solution. Crystals, 13(2), 211. https://doi.org/10.3390/cryst13020211
Tian, L., Zhang, J., Shi, H., Li, N., & Ping, Q. (2016). Adsorption of malachite green by diatomite: Equilibrium isotherms and kinetic studies. Journal of Dispersion Science and Technology, 37, 1059-1066. https://doi.org/10.1080/01932691.2015.1080610
Tehrani-Bagha, A. R., Nikkar, H., Mahmoodi, N. M., Markazi, M., & Menger, F. M. (2011). The sorption of cationic dyes onto kaolin: Kinetic, isotherm and thermodynamic studies. Desalination, 266(1-3), 274-280. https://doi.org/10.1016/j.desal.2010.08.036
Ukkund, S. J., Puthiyillam, P., Alshehri, H. M., Goodarzi, M., Taqui, S. N., Anqi, A. E., Safaei, M. R., Ali, M. A., Syed, U. T., Mir, R. A., Elfasakhany, A., Eed, E. M., Siddiqui, M. I. H., Mokashi, I., & Soudagar, M. E. M. (2021). Adsorption method for the remediation of brilliant green dye using halloysite nanotube: Isotherm, kinetic and modeling studies. Applied Sciences, 11, 8088. https://doi.org/10.3390/app11178088
Ullah, S., Ur Rahman, A., Ullah, F., Rashid, A., Arshad, T., Viglašová, E., Galamboš, M., Mahmoodi, M., & Ullah, H. (2021). Adsorption of malachite green dye onto mesoporous natural inorganic clays: Their equilibrium isotherm and kinetics studies. Water, 13(7), 965. https://doi.org/10.3390/w13070965
Uygun, O., Güven, R., & Çakal, G. Ö., (2023). Adsorptive removal of stable and radioactive Pb (II) isotopes from aqueous solution using bentonite, zeolite and perlite: Characterization, isotherm and thermodynamic studies. Clay Minerals, 58(2), 195-209. https://doi.org/10.1180/clm.2023.18
Vhahangwele, M., & Mugera, G. (2015). The potential of ball-milled South African bentonite clay for attenuation of heavy metals from acidic wastewater: Simultaneous sorption of Co2+, Cu2+, Ni2+, Pb2+ and Zn2+ ions. Journal of Environmental Chemical Engineering, 3, 2416-2425. https://doi.org/10.1016/j.jece.2015.08.016
Vithalkar, S., Jugade, R. M., & Saravanan, D. (2022). Adsorption of brilliant green dye by used-tea-powder: Equilibrium, kinetics and thermodynamics studies. Water Infrastructure, Ecosystems and Society, 71(10), 1148-1158. https://doi.org/10.2166/aqua.2022.076
Vojnović, B., Cetina, M., Franjković, P., & Sutlović, A. (2022). Influence of initial ph value on the adsorption of reactive black 5 dye on powdered activated carbon: Kinetics, mechanisms, and thermodynamics. Molecules, 27(4), 1349. https://doi.org/10.3390/molecules27041349
Waghmare, C., Ghodmare, S., Ansari, K., Alfaisal, F. M., Alam, S., Khan, M. A., & Ezaier, Y. (2024). Adsorption of methylene blue dye onto phosphoric acid-treated pomegranate peel adsorbent: Kinetic and thermodynamic studies. Desalination and Water Treatment, 318, 100406. https://doi.org/10.1016/j.dwt.2024.100406
Zhu, Y., Yi, B., Yuan, Q., Wu, Y., Wang, M., & Yan, S. (2018). Removal of methylene blue from aqueous solution by cattle manure-derived low temperature biochar. RSC Advances, 8(36), 19917-19929. https://doi.org/10.1039/c8ra03018a