Acid-Activated Natural Clay for Fe(III) Adsorption: An Integrated Study of Mechanisms, Kinetics, and Thermodynamics
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Keywords:
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Adsorption, Fe(III), Natural Clay, Kinetics, Thermodynamics
Abstract
The increasing contamination of water by Fe(III) ions from industrial activities, particularly in nickel-producing regions such as Morowali, presents serious environmental and public health concerns. Among various treatment approaches, adsorption stands out as an efficient and cost-effective method, especially using natural clay modified by acid treatment. This study aims to investigate the characterization, adsorption kinetics, and thermodynamic behavior of Fe(III) removal using acid-modified natural clay (NC) derived from Morowali. The clay was activated using sulfuric acid (H2SO4), followed by physicochemical characterization and batch adsorption experiments to assess its removal performance. Adsorption kinetics were analyzed using Pseudo-First Order (PFO), Pseudo-Second Order (PSO), Intraparticle Diffusion (IPD), and Liquid Film Diffusion (LFD) models to elucidate the adsorption mechanism. Furthermore, thermodynamic parameters such as Gibbs free energy (deltaG), enthalpy (deltaH), and entropy (deltaS) were calculated to determine the nature of the adsorption process. The results showed that NC exhibited a considerable adsorption capacity for Fe(III), with PSO providing the best kinetic fit, indicating chemisorption control. Thermodynamic analysis confirmed the spontaneous and endothermic nature of the process. These findings demonstrate the potential of acid-modified clay from Morowali as a low-cost and locally available adsorbent, contributing to sustainable water treatment strategies in industrial regions.
References
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Al-Odayni, A. B., F. S. Alsubaie, N. A. Y. Abdu, H. M. Al-Kahtani, and W. S. Saeed (2023). Adsorption Kinetics of Methyl Orange from Model Polluted Water onto N-Doped Activated Carbons Prepared from N-Containing Polymers. Polymers, 15(9); 1983
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Benjelloun, M., Y. Miyah, G. Akdemir Evrendilek, F. Zerrouq, and S. Lairini (2021). Recent Advances in Adsorption Kinetic Models: Their Application to Dye Types. Arabian Journal of Chemistry, 14(4); 103031
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Billah, R. E. K., Y. Haddaji, O. Goudali, M. Agunaou, and A. Soufiane (2021). Removal and Regeneration of Iron (III) from Water Using New Treated Fluorapatite Extracted from Natural Phosphate as Adsorbent. Biointerface Research in Applied Chemistry, 11(5); 13130–13140
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Islam, M. Z. and M. G. Mostafa (2024). Iron, Manganese, and Lead Contamination in Groundwater of Bangladesh: A Review. Water Practice and Technology, 19(3); 745–760
Kalabegashvili, N., G. Balarjishvili, D. Ioseliani, L. Samkharadze, N. Nonikashvili, and I. Mikadze (2022). Iron (III) Adsorption on Perlite. World Journal of Advanced Research and Reviews, 15(1); 644–650
Khatri, N., S. Tyagi, and D. Rawtani (2017). Recent Strategies for the Removal of Iron from Water: A Review. Journal of Water Process Engineering, 19(13); 291–304
Kulkarni, S. J. (2016). A Review on Studies and Research on Iron Removal. International Journal of Science and Healthcare Research, 1(2); 49
Kumar, R., P. Sharma, P. K. Sharma, P. K. Rose, R. K. Singh, N. Kumar, P. K. Sahoo, J. P. Maity, A. Ghosh, M. Kumar, P. Bhattacharya, and A. Pandey (2023). Rice Husk Biochar — A Novel Engineered Bio-Based Material for Transforming Groundwater-Mediated Fluoride Cycling in Natural Environments. Journal of Environmental Management, 343; 118222
Langeroodi, N. S., Z. Farhadravesh, and A. D. Khalaji (2018). Optimization of Adsorption Parameters for Fe(III) Ions Removal from Aqueous Solutions by Transition Metal Oxide Nanocomposite. Green Chemistry Letters and Reviews, 11(4); 404–413
Latunde-Dada, G. O. (2024). Iron Intake and Human Health. Nutrients, 16(2); 206
Li, Z., Z. Zheng, H. Li, D. Xu, X. Li, and L. Xiang (2023). Review on Rice Husk Biochar as an Adsorbent for Soil and. Plants, 12(1524); 1–19
Menkiti, M., I. Ezemagu, and S. Singaraju (2018). Focus on Adsorptive Equilibrium, Kinetics and Thermodynamic Components of Petroleum Produced Water Biocoagulation Using Novel Tympanotonos Fuscatus Extract. Petroleum, 4(1); 56–64
Middea, A., L. d. S. Spinelli, F. G. de Souza Junior, T. d. L. A. P. Fernandes, L. C. de Lima, V. M. T. S. Barthem, O. d. F. M. Gomes, and R. Neumann (2024). Removal of Fe³? Ions from Aqueous Solutions by Adsorption on Natural Eco-Friendly Brazilian Palygorskites. Mining, 4(1); 37–57
Mopoung, S., P. Moonsri, W. Palas, and S. Khumpai (2015). Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III) Adsorption from Aqueous Solution. Scientific World Journal, 2015(1); 415961
Nahiun, K., B. Sarker, K. N. Keya, F. I. Mahir, S. Shahida, and R. A. Khan (2021). A Review on the Methods of Industrial Waste Water Treatment. Scientific Review, 73; 20–31
Ngkoimani, L. O. and M. Chaerul (2017). Impacts of Nickel Laterite Post-Mining Activities on the Level of Heavy Metal Contamination in River Sediments. Advances in Social Science, Education and Humanities Research (ASSEHR), 149(Icest); 240–242
Oladimeji, T. E., M. Oyedemi, M. E. Emetere, O. Agboola, J. B. Adeoye, and O. A. Odunlami (2024). Review on the Impact of Heavy Metals from Industrial Wastewater Effluent and Removal Technologies. Heliyon, 10(23); e40370
Osmi?, S., A. Odobaši?, and S. Begi? (2024). The Influence of Acid Activation on Surface Characteristics of Natural Bentonite. International Research Journal of Pure and Applied Chemistry, 25(5); 35–42
Pakade, V. E., N. T. Tavengwa, and L. M. Madikizela (2019). Recent Advances in Hexavalent Chromium Removal from Aqueous Solutions by Adsorptive Methods. RSC Advances, 9(45); 26142–26164
Palapa, N. R., A. Amri, and Y. Hanifah (2023). Potential Indonesian Rice Husk for Wastewater Treatment: Agricultural Waste Preparation and Dye Removal Application. Indonesian Journal of Environmental Management and Sustainability, 7(4); 160–165
Purnamasari, I. and E. Supraptiah (2017). Adsorption Kinetics of Fe and Mn with Using Fly Ash from PT Semen Baturaja in Acid Mine Drainage. Indonesian Journal of Environmental Management and Sustainability, 1(1); 17–20
Raji, Z., A. Karim, A. Karam, and S. Khalloufi (2023). Adsorption of Heavy Metals: Mechanisms, Kinetics, and Applications of Various Adsorbents in Wastewater Remediation — A Review. Waste, 1(3); 775–805
Rosa, M. S. L., T. Knoerzer, F. C. Figueiredo, and J. R. dos Santos Júnior (2020). Clarification of Used Lubricating Oils by Application of Chemically-Modified Clays. Ceramica, 66(378); 130–136
Salam, M. A., R. M. El-Shishtawy, and A. Y. Obaid (2014). Synthesis of Magnetic Multi-Walled Carbon Nanotubes/Magnetite/Chitin Magnetic Nanocomposite for the Removal of Rose Bengal from Real and Model Solution. Journal of Industrial and Engineering Chemistry, 20(5); 3559–3567
Satchawan, S., P. Phuengphai, A. Ratanamanee, and N. Meethong (2022). Kinetic and Equilibrium Studies of Fe(III) Sorption from an Aqueous Solution Using Palmyra Palm Fruit Fibres as a Biosorbent. Applied Sciences, 12(20)
Sirotiak, M., B. Alica, and L. Blinová (2014). UV-Vis Spectrophotometric Determinations of Selected Elements in Modelled Aqueous Solutions. Journal of Environmental Protection, Safety, Education and Management, 2(3); 75–87
Song, P. N., J. G. Mahy, C. Calberg, A. Farcy, J. Caucheteux, N. Fagel, and S. D. Lambert (2023). Influence of Thermal and Acidic Treatments on the Morphology of a Natural Kaolinitic Clay Mineral. Results in Surfaces and Interfaces, 12(July); 100131
Thinojah, T. and B. Ketheesan (2022). Iron Removal from Groundwater Using Granular Activated Carbon Filters by Oxidation Coupled with the Adsorption Process. Journal of Water and Climate Change, 13(5); 1985–1994
Tran, H. N. (2023). Applying Linear Forms of Pseudo-Second-Order Kinetic Model for Feasibly Identifying Errors in the Initial Periods of Time-Dependent Adsorption Datasets. Water (Switzerland), 15(6); 1231
Wang, B., J. Lan, C. Bo, B. Gong, and J. Ou (2023). Adsorption of Heavy Metal onto Biomass-Derived Activated Carbon: Review. RSC Advances, 13(7); 4275–4302
Wang, P., X. Shen, S. Qiu, L. Zhang, Y. Ma, and J. Liang (2024). Clay-Based Materials for Heavy Metals Adsorption: Mechanisms, Advancements, and Future Prospects in Environmental Remediation. Crystals, 14(12); 1046
Xie, S., L. Huang, C. Su, J. Yan, Z. Chen, M. Li, M. Du, and H. Zhang (2024). Application of Clay Minerals as Adsorbents for Removing Heavy Metals from the Environment. Green and Smart Mining Engineering, 1(3); 249–261
Yang, J., B. Huang, and M. Lin (2020). Adsorption of Hexavalent Chromium from Aqueous Solution by a Chitosan/Bentonite Composite: Isotherm, Kinetics, and Thermodynamics Studies. Journal of Chemical and Engineering Data, 65(5); 2751–2763
Zein, R., Y. Prestica, D. Deswati, and P. Ramadhani (2023). Utilization of Coffee Peel Waste as Biosorbent for Rhodamine B Dye. Indonesian Journal of Environmental Management and Sustainability, 9(1); 36–45
Šuránek, M., Z. Melichová, M. M. Mirkovi?, M. Ivanovi?, V. B. Pavlovi?, L. Kljajevi?, and S. Nenadovi? (2023). The Study of Cu(II) Adsorption onto Synthetically Modified Geopolymers. Sustainability (Switzerland), 15(4); 2869
Abdel-Ghafar, H. M., E. A. Abdel-Aal, and B. E. El Anadouli (2020). Iron Removal from Ground Water Using Egyptian Cost-Effective Clay Minerals. Applied Chemical Engineering, 3(1); 23–30
Adawiyah, R., N. Yuliasari, Y. Hanifah, K. Alawiyah, and N. R. Palapa (2021). Utilizing Areca catechu L. Fruit Peel Derived Biochar and Hydrochar for. Indonesian Journal of Environmental Management and Sustainability, 8(4); 135–144
Afandy, M. A. and F. D. I. Sawali (2024). Effect of Concentration on Kinetics and Thermodynamics Parameter in the Cu(II) Removal by Activated Zeolite. Jurnal Integrasi Proses, 13(2); 174–183
Al-Odayni, A. B., F. S. Alsubaie, N. A. Y. Abdu, H. M. Al-Kahtani, and W. S. Saeed (2023). Adsorption Kinetics of Methyl Orange from Model Polluted Water onto N-Doped Activated Carbons Prepared from N-Containing Polymers. Polymers, 15(9); 1983
Alsaiari, R., I. Shedaiwa, F. A. Al-Qadri, E. M. Musa, H. Alqahtani, F. Alkorbi, N. A. Alsaiari, and M. M. Mohamed (2024). Peganum Harmala L. Plant as Green Non-Toxic Adsorbent for Iron Removal from Water. Archives of Environmental Protection, 50(1); 3–12
Auta, M. and B. H. Hameed (2013). Acid Modified Local Clay Beads as Effective Low-Cost Adsorbent for Dynamic Adsorption of Methylene Blue. Journal of Industrial and Engineering Chemistry, 19(4); 1153–1161
Bahabadi, F. N., M. H. Farpoor, and M. H. Mehrizi (2016). Removal of Cd, Cu and Zn Ions from Aqueous Solutions Using Natural and Fe Modified Sepiolite, Zeolite and Palygorskite Clay Minerals. Water Science and Technology, 75(2); 340–349
Bakalár, T., M. Ka?uchová, A. Girová, H. Pavolová, R. Hromada, and Z. Hajduová (2020). Characterization of Fe(III) Adsorption Onto Zeolite and Bentonite. International Journal of Environmental Research and Public Health, 17(16); 1–13
Benjelloun, M., Y. Miyah, G. Akdemir Evrendilek, F. Zerrouq, and S. Lairini (2021). Recent Advances in Adsorption Kinetic Models: Their Application to Dye Types. Arabian Journal of Chemistry, 14(4); 103031
Bennour, H. A. M. (2017). Effect of Acid Activation on Adsorption of Iron and Manganese Using Libyan Bentonite Clay. Chemical Science Transactions, 6(2); 209–218
Billah, R. E. K., Y. Haddaji, O. Goudali, M. Agunaou, and A. Soufiane (2021). Removal and Regeneration of Iron (III) from Water Using New Treated Fluorapatite Extracted from Natural Phosphate as Adsorbent. Biointerface Research in Applied Chemistry, 11(5); 13130–13140
Bullen, J. C., S. Saleesongsom, K. Gallagher, and D. J. Weiss (2021). A Revised Pseudo-Second-Order Kinetic Model for Adsorption, Sensitive to Changes in Adsorbate and Adsorbent Concentrations. Langmuir, 37(10); 3189–3201
Caccamo, M. T., G. Mavilia, L. Mavilia, D. Lombardo, and S. Magazù (2020). Self-Assembly Processes in Hydrated Montmorillonite by FTIR Investigations. Materials, 13(5); 1100
Costea, I. F., A.-M. Ceoromila, A. Tabacaru, and G. Carac (2024). Investigation of Chitosan Flakes in the Adsorption of Fe(III) Ions from Acidic Solution. Revista de Chimie, 75(2); 1–10
Das, D. and B. K. Nandi (2019). Removal of Fe(II) Ions from Drinking Water Using Electrocoagulation (EC) Process: Parametric Optimization and Kinetic Study. Journal of Environmental Chemical Engineering, 7(3); 103116
Elewa, A. M., A. A. Amer, M. F. Attallah, H. A. Gad, Z. A. M. Al-Ahmed, and I. A. Ahmed (2023). Chemically Activated Carbon Based on Biomass for Adsorption of Fe(III) and Mn(II) Ions from Aqueous Solution. Materials, 16(3); 1251
Enaime, G., A. Bacaoui, A. Yaacoubi, and M. Lübken (2020). Biochar for Wastewater Treatment—Conversion Technologies and Applications. Applied Sciences, 10(10); 3492
Guo, X., A. Liu, J. Lu, X. Niu, M. Jiang, Y. Ma, X. Liu, and M. Li (2020). Adsorption Mechanism of Hexavalent Chromium on Biochar: Kinetic, Thermodynamic, and Characterization Studies. ACS Omega, 5(42); 27323–27331
Herrera, K., L. F. Morales, N. A. Tarazona, R. Aguado, and J. F. Saldarriaga (2022). Use of Biochar from Rice Husk Pyrolysis: Part A: Recovery as an Adsorbent in the Removal of Emerging Compounds. ACS Omega, 7(9); 7625–7637
Inyinbor, A. A., F. A. Adekola, and G. A. Olatunji (2016). Kinetics, Isotherms and Thermodynamic Modeling of Liquid Phase Adsorption of Rhodamine B Dye Onto Raphia hookerie Fruit Epicarp. Water Resources and Industry, 15; 14–27
Islam, M. Z. and M. G. Mostafa (2024). Iron, Manganese, and Lead Contamination in Groundwater of Bangladesh: A Review. Water Practice and Technology, 19(3); 745–760
Kalabegashvili, N., G. Balarjishvili, D. Ioseliani, L. Samkharadze, N. Nonikashvili, and I. Mikadze (2022). Iron (III) Adsorption on Perlite. World Journal of Advanced Research and Reviews, 15(1); 644–650
Khatri, N., S. Tyagi, and D. Rawtani (2017). Recent Strategies for the Removal of Iron from Water: A Review. Journal of Water Process Engineering, 19(13); 291–304
Kulkarni, S. J. (2016). A Review on Studies and Research on Iron Removal. International Journal of Science and Healthcare Research, 1(2); 49
Kumar, R., P. Sharma, P. K. Sharma, P. K. Rose, R. K. Singh, N. Kumar, P. K. Sahoo, J. P. Maity, A. Ghosh, M. Kumar, P. Bhattacharya, and A. Pandey (2023). Rice Husk Biochar — A Novel Engineered Bio-Based Material for Transforming Groundwater-Mediated Fluoride Cycling in Natural Environments. Journal of Environmental Management, 343; 118222
Langeroodi, N. S., Z. Farhadravesh, and A. D. Khalaji (2018). Optimization of Adsorption Parameters for Fe(III) Ions Removal from Aqueous Solutions by Transition Metal Oxide Nanocomposite. Green Chemistry Letters and Reviews, 11(4); 404–413
Latunde-Dada, G. O. (2024). Iron Intake and Human Health. Nutrients, 16(2); 206
Li, Z., Z. Zheng, H. Li, D. Xu, X. Li, and L. Xiang (2023). Review on Rice Husk Biochar as an Adsorbent for Soil and. Plants, 12(1524); 1–19
Menkiti, M., I. Ezemagu, and S. Singaraju (2018). Focus on Adsorptive Equilibrium, Kinetics and Thermodynamic Components of Petroleum Produced Water Biocoagulation Using Novel Tympanotonos Fuscatus Extract. Petroleum, 4(1); 56–64
Middea, A., L. d. S. Spinelli, F. G. de Souza Junior, T. d. L. A. P. Fernandes, L. C. de Lima, V. M. T. S. Barthem, O. d. F. M. Gomes, and R. Neumann (2024). Removal of Fe³? Ions from Aqueous Solutions by Adsorption on Natural Eco-Friendly Brazilian Palygorskites. Mining, 4(1); 37–57
Mopoung, S., P. Moonsri, W. Palas, and S. Khumpai (2015). Characterization and Properties of Activated Carbon Prepared from Tamarind Seeds by KOH Activation for Fe(III) Adsorption from Aqueous Solution. Scientific World Journal, 2015(1); 415961
Nahiun, K., B. Sarker, K. N. Keya, F. I. Mahir, S. Shahida, and R. A. Khan (2021). A Review on the Methods of Industrial Waste Water Treatment. Scientific Review, 73; 20–31
Ngkoimani, L. O. and M. Chaerul (2017). Impacts of Nickel Laterite Post-Mining Activities on the Level of Heavy Metal Contamination in River Sediments. Advances in Social Science, Education and Humanities Research (ASSEHR), 149(Icest); 240–242
Oladimeji, T. E., M. Oyedemi, M. E. Emetere, O. Agboola, J. B. Adeoye, and O. A. Odunlami (2024). Review on the Impact of Heavy Metals from Industrial Wastewater Effluent and Removal Technologies. Heliyon, 10(23); e40370
Osmi?, S., A. Odobaši?, and S. Begi? (2024). The Influence of Acid Activation on Surface Characteristics of Natural Bentonite. International Research Journal of Pure and Applied Chemistry, 25(5); 35–42
Pakade, V. E., N. T. Tavengwa, and L. M. Madikizela (2019). Recent Advances in Hexavalent Chromium Removal from Aqueous Solutions by Adsorptive Methods. RSC Advances, 9(45); 26142–26164
Palapa, N. R., A. Amri, and Y. Hanifah (2023). Potential Indonesian Rice Husk for Wastewater Treatment: Agricultural Waste Preparation and Dye Removal Application. Indonesian Journal of Environmental Management and Sustainability, 7(4); 160–165
Purnamasari, I. and E. Supraptiah (2017). Adsorption Kinetics of Fe and Mn with Using Fly Ash from PT Semen Baturaja in Acid Mine Drainage. Indonesian Journal of Environmental Management and Sustainability, 1(1); 17–20
Raji, Z., A. Karim, A. Karam, and S. Khalloufi (2023). Adsorption of Heavy Metals: Mechanisms, Kinetics, and Applications of Various Adsorbents in Wastewater Remediation — A Review. Waste, 1(3); 775–805
Rosa, M. S. L., T. Knoerzer, F. C. Figueiredo, and J. R. dos Santos Júnior (2020). Clarification of Used Lubricating Oils by Application of Chemically-Modified Clays. Ceramica, 66(378); 130–136
Salam, M. A., R. M. El-Shishtawy, and A. Y. Obaid (2014). Synthesis of Magnetic Multi-Walled Carbon Nanotubes/Magnetite/Chitin Magnetic Nanocomposite for the Removal of Rose Bengal from Real and Model Solution. Journal of Industrial and Engineering Chemistry, 20(5); 3559–3567
Satchawan, S., P. Phuengphai, A. Ratanamanee, and N. Meethong (2022). Kinetic and Equilibrium Studies of Fe(III) Sorption from an Aqueous Solution Using Palmyra Palm Fruit Fibres as a Biosorbent. Applied Sciences, 12(20)
Sirotiak, M., B. Alica, and L. Blinová (2014). UV-Vis Spectrophotometric Determinations of Selected Elements in Modelled Aqueous Solutions. Journal of Environmental Protection, Safety, Education and Management, 2(3); 75–87
Song, P. N., J. G. Mahy, C. Calberg, A. Farcy, J. Caucheteux, N. Fagel, and S. D. Lambert (2023). Influence of Thermal and Acidic Treatments on the Morphology of a Natural Kaolinitic Clay Mineral. Results in Surfaces and Interfaces, 12(July); 100131
Thinojah, T. and B. Ketheesan (2022). Iron Removal from Groundwater Using Granular Activated Carbon Filters by Oxidation Coupled with the Adsorption Process. Journal of Water and Climate Change, 13(5); 1985–1994
Tran, H. N. (2023). Applying Linear Forms of Pseudo-Second-Order Kinetic Model for Feasibly Identifying Errors in the Initial Periods of Time-Dependent Adsorption Datasets. Water (Switzerland), 15(6); 1231
Wang, B., J. Lan, C. Bo, B. Gong, and J. Ou (2023). Adsorption of Heavy Metal onto Biomass-Derived Activated Carbon: Review. RSC Advances, 13(7); 4275–4302
Wang, P., X. Shen, S. Qiu, L. Zhang, Y. Ma, and J. Liang (2024). Clay-Based Materials for Heavy Metals Adsorption: Mechanisms, Advancements, and Future Prospects in Environmental Remediation. Crystals, 14(12); 1046
Xie, S., L. Huang, C. Su, J. Yan, Z. Chen, M. Li, M. Du, and H. Zhang (2024). Application of Clay Minerals as Adsorbents for Removing Heavy Metals from the Environment. Green and Smart Mining Engineering, 1(3); 249–261
Yang, J., B. Huang, and M. Lin (2020). Adsorption of Hexavalent Chromium from Aqueous Solution by a Chitosan/Bentonite Composite: Isotherm, Kinetics, and Thermodynamics Studies. Journal of Chemical and Engineering Data, 65(5); 2751–2763
Zein, R., Y. Prestica, D. Deswati, and P. Ramadhani (2023). Utilization of Coffee Peel Waste as Biosorbent for Rhodamine B Dye. Indonesian Journal of Environmental Management and Sustainability, 9(1); 36–45
Šuránek, M., Z. Melichová, M. M. Mirkovi?, M. Ivanovi?, V. B. Pavlovi?, L. Kljajevi?, and S. Nenadovi? (2023). The Study of Cu(II) Adsorption onto Synthetically Modified Geopolymers. Sustainability (Switzerland), 15(4); 2869
Authors
Afandy, M. A., Herliawan, D. J. H., Nirwansyah, & Sawali, F. D. I. (2025). Acid-Activated Natural Clay for Fe(III) Adsorption: An Integrated Study of Mechanisms, Kinetics, and Thermodynamics. Indonesian Journal of Environmental Management and Sustainability, 9(3), 143-155. https://doi.org/10.26554/ijems.2025.9.3.143-155
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