Vol. 25, No. 3 (2026), IA26888 https://doi.org/10.24275/rmiq/IA26888


Mechanistic insights into metformin sorption onto natural, sodium-exchanged, HDTMA-modified, and cerium-loaded clinoptilolite zeolites


 

Authors

A.M. Dávila-Estrada, J.J. Ramírez-García


Abstract

Metformin is a persistent antidiabetic drug frequently detected in aquatic environments due to its incomplete removal in conventional wastewater treatment plants. In this study, the dominant sorption mechanisms of metformin onto natural clinoptilolite (ZN), sodium-conditioned zeolite (ZNa), hexadecyltrimethylammonium bromide-modified zeolite (ZMS), and cerium-loaded zeolite (ZCe) were investigated. Experiments were conducted at intrinsic pH (5–6), where metformin is predominantly present in its protonated form. The materials were characterized by Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (SEM–EDS), Thermogravimetric Analysis (TGA), CHNS elemental analysis, and point of zero charge (pHpzc).
Kinetic assays performed at 100 mg L-1 and 25 °C showed that ZNa exhibited the highest sorption capacity (2.42 mg g-1), followed by ZMS (1.90 mg g-1), ZN (1.62 mg g-1), and ZCe (1.23 mg g-1). The Elovich model provided the best fit (R2 > 0.90), indicating heterogeneous, activation-controlled sorption. The release of Na+ provided qualitative evidence supporting cation exchange as the predominant sorption mechanism under the evaluated conditions.

Overall, sodium conditioning enhanced metformin sorption by increasing the availability of exchangeable Na+ sites.


Keywords

Clinoptilolite, cation exchange, metformin, pharmaceutical pollution, sorption mechanism.


References

  • Al Abri, S., Rogov, A., Aliasghari, S., Bendo, A., Matthews, A., Yerokhin, A., & Mingo, B. (2024). In-situ incorporation of Ce-zeolite during soft sparking plasma electrolytic oxidation. Journal of Materials Research and Technology, 30, 2365–2376. https://doi.org/10.1016/j.jmrt.2024.04.011
  • Alcantara-Cobos, A., Solache-Rios, M., & Gutiérrez-Segura, E. (2019). Nobel Materials (ZnO Nanoparticles and ZnO Nanoparticles Supported on a Zeolite) for the Removal of Tartrazine from Aqueous Solutions. Water, Air, and Soil Pollution, 230(8). https://doi.org/10.1007/s11270-019-4252-4
  • Alvarez-García, S., Ramírez-García, J. J., Granados-Correa, F., & Sánchez-Meza, J. C. (2020). Structural and textural influences of surfactant-modified zeolitic materials over the methamidophos adsorption behavior. Separation Science and Technology (Philadelphia), 55(4), 619–634. https://doi.org/10.1080/01496395.2019.1568476
  • Bajda, T., Grela, A., Pamuła, J., Kuc, J., Klimek, A., Matusik, J., Franus, W., Alagarsamy, S. K. K., Danek, T., & Gara, P. (2024). Using Zeolite Materials to Remove Pharmaceuticals from Water. Materials, 17(15). https://doi.org/10.3390/ma17153848
  • Barczyk, K., Mozgawa, W., & Król, M. (2014). Studies of anions sorption on natural zeolites. Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 133, 876–882. https://doi.org/10.1016/j.saa.2014.06.065
  • Biblioteca, I., Sambucci, M., & Valente, M. (2023). Zeolite-Clinoptilolite conditioning for improved heavy metals ions removal: A preliminary assessment. Ceramics International, 49(23), 39649–39656. https://doi.org/10.1016/j.ceramint.2023.09.319
  • Chenet, T., Mancinelli, M., Sarti, E., Costa, V., D’Anna, C., Martucci, A., & Pasti, L. (2024). Competitive Adsorption of 4-Hydroxybenzaldehyde and Toluene onto High Silica Zeolites. Environmental Processes, 11(3). https://doi.org/10.1007/s40710-024-00726-2
  • Díaz-Nava, M. C., Olguín, M. T., Solache-Ríos, M., Alarcón-Herrera, M. T., & Aguilar-Elguezabal, A. (2005). Characterization and improvement of ion exchange capacities of Mexican clinoptilolite-rich tuffs. Journal of Inclusion Phenomena, 51(3–4), 231–240. https://doi.org/10.1007/s10847-004-6716-3
  • Doula, M. K. (2007). Synthesis of a clinoptilolite-Fe system with high Cu sorption capacity. Chemosphere, 67(4), 731–740. https://doi.org/10.1016/j.chemosphere.2006.10.072
  • Ferri, B. B., Wernke, G., Resende, J. F., Ribeiro, A. C., Cusioli, L. F., Bergamasco, R., & Vieira, M. F. (2024). Natural zeolite as adsorbent for metformin removal from aqueous solutions: Adsorption and regeneration properties. Desalination and Water Treatment, 320. https://doi.org/10.1016/j.dwt.2024.100602
  • Flores-Alamo, N., Vázquez-Méndez, J. I., Solache-Ríos, M. J., Cuellar-Robles, F., & Carreño-de-León, M. C. (2025). Removal of fluoride ions from aqueous solutions and water for human consumption by a surfactant modified zeolite. Revista Mexicana de Ingeniería Química, 24(2), Article IA25491. https://doi.org/10.24275/rmiq/IA25491
  • Godoy, A. A., Domingues, I., Arsénia Nogueira, A. J., & Kummrow, F. (2018). Ecotoxicological effects, water quality standards and risk assessment for the anti-diabetic metformin. Environmental Pollution, 243, 534–542. https://doi.org/10.1016/j.envpol.2018.09.031
  • González-Ortiz, A., Ramírez-García, J. J., & Solache-Ríos, M. J. (2018). Kinetic and Thermodynamic Behavior on the Sorption of Clindamycin from an Aqueous Medium by Modified Surface Zeolitic Tuffs. Water, Air, and Soil Pollution, 229(10). https://doi.org/10.1007/s11270-018-3970-3
  • He, Y., Zhang, Y., & Ju, F. (2022). Metformin Contamination in Global Waters: Biotic and Abiotic Transformation, Byproduct Generation and Toxicity, and Evaluation as a Pharmaceutical Indicator. In Environmental Science and Technology (Vol. 56, Number 19, pp. 13528–13545). American Chemical Society. https://doi.org/https://doi.org/10.1021/acs.est.2c02495
  • Helmi, M., Hemmati, A., & Ghaemi, A. (2024). Clinoptilolite and MCM-41 impregnated with chitosan as a green novel adsorbent for CO2 capture. Case Studies in Chemical and Environmental Engineering, 9. https://doi.org/10.1016/j.cscee.2024.100764
  • Ho, Y. S., & Mckay, G. (1999). Pseudo-second order model for sorption processes. In Process Biochemistry (Vol. 34). https://doi.org/https://doi.org/10.1016/S0032-9592(98)00112-5
  • Hosseini, M., Haghighi, M., Kahforoushan, D., & Zarrabi, M. (2017). Sono-dispersion of ceria and palladium in preparation and characterization of Pd/Al2O3-clinoptilolite-CeO2 nanocatalyst for treatment of polluted air via low temperature VOC oxidation. Process Safety and Environmental Protection, 106, 284–293. https://doi.org/10.1016/j.psep.2016.06.028
  • Inglezakis, V. J., Stylianou, M., & Loizidou, M. (2010). Ion exchange and adsorption equilibrium studies on clinoptilolite, bentonite and vermiculite. Journal of Physics and Chemistry of Solids, 71(3), 279–284. https://doi.org/10.1016/j.jpcs.2009.12.077
  • Jiang, N., Shang, R., Heijman, S. G. J., & Rietveld, L. C. (2018). High-silica zeolites for adsorption of organic micro-pollutants in water treatment: A review. In Water Research (Vol. 144, pp. 145–161). Elsevier Ltd. https://doi.org/https://doi.org/10.1016/j.watres.2018.07.017
  • Khader, E. H., Mohammed, T. J., Mirghaffari, N., Salman, A. D., Juzsakova, T., & Abdullah, T. A. (2022). Removal of organic pollutants from produced water by batch adsorption treatment. Clean Technologies and Environmental Policy, 24(2), 713–720. https://doi.org/10.1007/s10098-021-02159-z
  • Król, M., Dechnik, J., Szymczak, P., Handke, B., Szumera, M., & Stoch, P. (2024). Thermal Behavior of Clinoptilolite. Crystals, 14(7). https://doi.org/10.3390/cryst14070646
  • Król, M., Koleżyński, A., & Mozgawa, W. (2021). Vibrational spectra of zeolite y as a function of ion exchange. Molecules, 26(2). https://doi.org/10.3390/molecules26020342
  • Kukwa, R. E., & Dann, S. E. (2019). Grafted zeolites for the removal of metal cations from crude oil hydrotreatment extract. Desalination and Water Treatment, 153, 136–144. https://doi.org/10.5004/dwt.2019.23881
  • Kuleyin, A. (2007). Removal of phenol and 4-chlorophenol by surfactant-modified natural zeolite. Journal of Hazardous Materials, 144(1–2), 307–315. https://doi.org/10.1016/j.jhazmat.2006.10.036
  • Leal-Perez, J. E., Almaral-Sanchez, J. L., Hurtado-Macias, A., Cortez-Valadez, M., Bórquez-Mendívil, A., García-Grajeda, B. A., Mendivil-Escalante, J. M., & Flores-Valenzuela, J. (2024). Structural and chemical analysis of Zn ion exchange in thermally modified zeolite A4. Revista Mexicana de Ingeniería Química, 23(3), Article Mat24264. https://doi.org/10.24275/rmiq/Mat24264
  • Li, Z., Yuansheng, D., & Hanlie, H. (2008). Transport of micelles of cationic surfactants through clinoptilolite zeolite. Microporous and Mesoporous Materials, 116(1–3), 473–477. https://doi.org/10.1016/j.micromeso.2008.05.006
  • Martucci, A., Pasti, L., Marchetti, N., Cavazzini, A., Dondi, F., & Alberti, A. (2012). Adsorption of pharmaceuticals from aqueous solutions on synthetic zeolites. Microporous and Mesoporous Materials, 148(1), 174–183. https://doi.org/10.1016/j.micromeso.2011.07.009
  • Mijailović, N. R., Nedić Vasiljević, B., Ranković, M., Milanović, V., & Uskoković-Marković, S. (2022). Environmental and Pharmacokinetic Aspects of Zeolite/Pharmaceuticals Systems—Two Facets of Adsorption Ability. In Catalysts (Vol. 12, Number 8). MDPI. https://doi.org/https://doi.org/10.3390/catal12080837
  • Misaelides, P. (2011). Application of natural zeolites in environmental remediation: A short review. Microporous and Mesoporous Materials, 144(1–3), 15–18. https://doi.org/10.1016/j.micromeso.2011.03.024
  • Momeni, S., Farrokhnia, M., Karimi, S., & Nabipour, I. (2016). Copper hydroxide nanostructure-modified carbon ionic liquid electrode as an efficient voltammetric sensor for detection of metformin: a theoretical and experimental study. Journal of the Iranian Chemical Society, 13(6), 1027–1035. https://doi.org/10.1007/s13738-016-0816-z
  • Montalvo, S., Guerrero, L., Borja, R., Sánchez, E., Milán, Z., Cortés, I., & Angeles de la la Rubia, M. (2012). Application of natural zeolites in anaerobic digestion processes: A review. In Applied Clay Science (Vol. 58, pp. 125–133). https://doi.org/https://doi.org/10.1016/j.clay.2012.01.013
  • Moshoeshoe, M., Silas Nadiye-Tabbiruka, M., & Obuseng, V. (2017). A Review of the Chemistry, Structure, Properties and Applications of Zeolites. American Journal of Materials Science, 2017(5), 196–221. https://doi.org/10.5923/j.materials.20170705.12
  • Naghash, A., & Nezamzadeh-Ejhieh, A. (2015). Comparison of the efficiency of modified clinoptilolite with HDTMA and HDP surfactants for the removal of phosphate in aqueous solutions. Journal of Industrial and Engineering Chemistry, 31, 185–191. https://doi.org/10.1016/j.jiec.2015.06.022
  • Nannu Shankar, S., Dinakaran, D. R., Chandran, D. K., Mantha, G., Srinivasan, B., & Nyayiru Kannaian, U. P. (2023). Adsorption kinetics, equilibrium and thermodynamics of a textile dye V5BN by a natural nanocomplex material: Clinoptilolite. Energy Nexus, 10. https://doi.org/10.1016/j.nexus.2023.100197
  • Nezamzadeh-Ejhieh, A., & Tavakoli-Ghinani, S. (2014). Effect of a nano-sized natural clinoptilolite modified by the hexadecyltrimethyl ammonium surfactant on cephalexin drug delivery. Comptes Rendus Chimie, 17(1), 49–61. https://doi.org/10.1016/j.crci.2013.07.009
  • Pérez Cordoves, A. I., Granda Valdés, M., Torres Fernández, J. C., Pina Luis, G., García-Calzón, J. A., & Díaz García, M. E. (2008). Characterization of the binding site affinity distribution of a surfactant-modified clinoptilolite. Microporous and Mesoporous Materials, 109(1–3), 38–48. https://doi.org/https://doi.org/10.1016/j.micromeso.2007.04.029
  • Perić, J., Trgo, M., & Vukojević Medvidović, N. (2004). Removal of zinc, copper and lead by natural zeolite - A comparison of adsorption isotherms. Water Research, 38(7), 1893–1899. https://doi.org/10.1016/j.watres.2003.12.035
  • Prajaputra, V., & Isnaini, N. (2023). Assessment of Metformin Stability and Its Removal from Water by Pumice-Based Zeolite. Jurnal Penelitian Pendidikan IPA, 9(7), 4909–4916. https://doi.org/10.29303/jppipa.v9i7.3965
  • Rožić, M., Ivanec Šipušić, D., Sekovanić, L., Miljanić, S., Ćurković, L., & Hrenović, J. (2009). Sorption phenomena of modification of clinoptilolite tuffs by surfactant cations. Journal of Colloid and Interface Science, 331(2), 295–301. https://doi.org/10.1016/j.jcis.2008.11.043
  • Saeedi, P., Petersohn, I., Salpea, P., Malanda, B., Karuranga, S., Unwin, N., Colagiuri, S., Guariguata, L., Motala, A. A., Ogurtsova, K., Shaw, J. E., Bright, D., & Williams, R. (2019). Global and regional diabetes prevalence estimates for 2019 and projections for 2030 and 2045: Results from the International Diabetes Federation Diabetes Atlas, 9th edition. Diabetes Research and Clinical Practice, 157. https://doi.org/10.1016/j.diabres.2019.107843
  • Salazar-Gil, K., Díaz-Nava, M. C., & Solache-Ríos, M. (2016). Removal of red 2 and yellow 6 by Zn- and-Na modified zeolitic tuffs in the presence of H2O2. Desalination and Water Treatment, 57(35), 16626–16632. https://doi.org/10.1080/19443994.2015.1079260
  • Serna-Galvis, E. A., Arboleda-Echavarría, J., Echavarría-Isaza, A., & Torres-Palma, R. A. (2024). Removal and elimination of pharmaceuticals in water using zeolites in diverse adsorption processes and catalytic advanced oxidation technologies—a critical review. In Environmental Science and Pollution Research (Vol. 31, Number 55, pp. 63427–63457). Springer. https://doi.org/https://doi.org/10.1007/s11356-024-35204-7
  • Shearer, L., Pap, S., & Gibb, S. W. (2022). Removal of pharmaceuticals from wastewater: A review of adsorptive approaches, modelling and mechanisms for metformin and macrolides. In Journal of Environmental Chemical Engineering (Vol. 10, Number 4). Elsevier Ltd. https://doi.org/https://doi.org/10.1016/j.jece.2022.108106
  • Torabian, A., Kazemian, H., Seifi, L., Bidhendi, G. N., Azimi, A. A., & Ghadiri, S. K. (2010). Removal of petroleum aromatic hydrocarbons by surfactant-modified natural zeolite: The effect of surfactant. Clean - Soil, Air, Water, 38(1), 77–83. https://doi.org/10.1002/clen.200900157
  • Tran, H. N., You, S. J., Hosseini-Bandegharaei, A., & Chao, H. P. (2017). Mistakes and inconsistencies regarding adsorption of contaminants from aqueous solutions: A critical review. Water Research, 120, 88–116. https://doi.org/10.1016/j.watres.2017.04.014
  • Wang, S., & Peng, Y. (2010). Natural zeolites as effective adsorbents in water and wastewater treatment. In Chemical Engineering Journal (Vol. 156, Number 1, pp. 11–24). https://doi.org/https://doi.org/10.1016/j.cej.2009.10.029
  • Weber, W. J., Jr., & Morris, J. C. (1963). Kinetics of adsorption on carbon from solution. Journal of the Sanitary Engineering Division, 89(2), 31–59. https://doi.org/10.1061/JSEDAI.0000430
  • Wingenfelder, U., Furrer, G., & Schulin, R. (2006). Sorption of antimonate by HDTMA-modified zeolite. Microporous and Mesoporous Materials, 95(1–3), 265–271. https://doi.org/10.1016/j.micromeso.2006.06.001
  • Zorita, S., Hallgren, P., & Mathiasson, L. (2008). Steroid hormone determination in water using an environmentally friendly membrane based extraction technique. Journal of Chromatography A, 1192(1), 1–8. https://doi.org/10.1016/j.chroma.2008.03.030