Simultaneous action of surfactant modified clinoptilolite: Adsorbent of dyes and antibacterial agent


  • Muhammad Syafiq Abd Aziz Universiti Teknologi Malaysia
  • Nik Ahmad Nizam Nik Malek Universiti Teknologi Malaysia
  • Siti Nabihan Ishak Universiti Teknologi Malaysia
  • Muhammad Hariz Asraf Universiti Teknologi Malaysia
  • Atieya Abdul Hadi Universiti Teknologi Malaysia
  • Muhammad Zulhilmi Amir Awaluddin Universiti Teknologi Malaysia



Clinoptilolite, surfactant modified zeolite, methylene blue, acid orange 7, antibacterial agent


In this study, the simultaneous action of surfactant modified clinoptilolite (SMC) as adsorbent for dyes and its antibacterial activity was investigated. Methylene blue (MB) and acid orange 7 (AO7) represent cationic and anionic dyes, respectively were used as adsorbate in this study and the antibacterial activity was studied against Gram-negative (Escherichia coli ATCC 11229) and Gram-positive bacteria (Staphylococcus aureus ATCC 6538 and Enterococcus faecalis ATCC 2921). Initially, natural zeolite clinoptilolite was modified with 3 different concentrations (0.1, 1.0 and 4.0 mM) of cationic surfactant hexadecyltrimethyl ammonium bromide (HDTMA-Br). The SMC samples were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), amount of HDTMA adsorbed and dispersion behaviour. Result from XRD shows that the HDTMA-Br molecules caused no effect on primary structure of the clinoptilolite since the clinoptilolite structure remained the same after modification with HDTMA-Br. Compared to the unmodified clinoptilolite, FTIR spectra of the SMC shows peak corresponds to C-H stretches which proved the attachment of HDTMA onto the clinoptilolite surfaces. In the dispersion behaviour study, SMC samples were located at the adjacent phase between the water and oil mixture. The amount of HDTMA-Br adsorbed onto the clinoptilolite increased with the increasing concentrations of the surfactant. The use of SMC as adsorbent and antibacterial agent were further studied against the ionic dyes and bacteria simultaneously. The results show that the adsorption capacity of SMC towards both ionic dyes increase with the increasing HDTMA-Br concentration. While for the antibacterial activity, the number of colony forming unit of bacteria seem to be highly reduced at the highest concentration of the HDTMA (4.0 mM) attached on the clinoptilolite. Hence, this study had shown that SMC has high adsorption capacity towards the ionic dyes at the same time reducing the growth of both Gram positive and negative bacteria in aquoes solution. 

Author Biographies

Muhammad Syafiq Abd Aziz, Universiti Teknologi Malaysia

Faculty of Biosciences and Medical Engineering

Nik Ahmad Nizam Nik Malek, Universiti Teknologi Malaysia

Faculty of Biosciences and Medical Engineering

Siti Nabihan Ishak, Universiti Teknologi Malaysia

Faculty of Biosciences and Medical Engineering

Muhammad Hariz Asraf, Universiti Teknologi Malaysia

Faculty of Biosciences and Medical Engineering

Atieya Abdul Hadi, Universiti Teknologi Malaysia

Faculty of Biosciences and Medical Engineering

Muhammad Zulhilmi Amir Awaluddin, Universiti Teknologi Malaysia

Faculty of Biosciences and Medical Engineering


Apreutesei, R. E., Catrinescu, C., Teodosiu, C. 2008. Surfactant-modified natural zeolites for environmental applications in water purification. Environmental Engineering and Management Journal, 7, 149-161.

Armağan, B., Turan, M., Ęlik, M. S. 2004. Equilibrium studies on the adsorption of reactive azo dyes into zeolite. Desalination, 170, 33-39.

Block, S. S. 2001. Disinfection, Sterilization, and Preservation. USA: Lippincott Williams & Wilkins.

Bowman, R. S., Sullivan, E. J., Li, Z. 2000. Uptake of Cations, Anions, and Nonpolar Organic Molecules by Surfactant-Modified Clinoptilolite-Rich Tuff. Natural Zeolites For The Third Millenium. International conference on the occurrence, properties, and utilization of natural zeolites. 1997.

De Frede Editore, Naples, Italy, 287-297.

Chaouati, N., Soualah, A., Chater, M. 2013. Adsorption of phenol from aqueous solution onto zeolites Y modified by silylation. Comptes Rendus

Chimie, 16, 222-228.

Cifuentes, A., Bernal, J. L., Diez-Masa, J. C. 1997. Determination of critical micelle concentration values using capillary electrophoresis instrumentation. Analytical Chemistry, 69, 4271-4274.

Clifton, L. A., Skoda, M. W., Le Brun, A. P., Ciesielski, F., Kuzmenko, I., Holt, S. A., Lakey, J. H. 2015. Effect of divalent cation removal on the structure of gram-negative bacterial outer membrane models. Langmuir, 31(1), 404-412.

Coa, F., Strauss, M., Clemente, Z., Neto, L. L. R., Lopes, J. R., Alencar, R. S., Souza, A. G., Alves, O. L., Castro, V. L. S. S., Barbieri, E., Martinez, D. S. T. 2017. Coating carbon nanotubes with humic acid using an eco-friendly mechanochemical method: Application for Cu(II) ions removal from water and aquatic ecotoxicity. Science of the Total Environment, 607, 1479-1486.

Ebrahiem, E. E., Al-Maghrabi, M. N., Mobarki, A. R. 2017. Removal of organic pollutants from industrial wastewater by applying photo-fenton oxidation technology. Arabian Journal of Chemistry, 10, S1674–S1679.

Erdogan, B. C. & Ulku, S. 2013. Removal of bacteria by clinoptilolite rich mineral and its surfactant modified forms. Journal of Porous Materials, 20, 1143-1151.

Goyal, N., Bulasara, V. K., Barman, S. 2018. Removal of emerging contaminants daidzein and coumestrol from water by nanozeolite beta modified with tetrasubstituted ammonium cation. Hazardous Waste and Hazardous Materials, 344, 417-430.

Humplik, T., Lee, J., O'Hern, S. C. 2011. Nanostructured materials for water desalination. Nanotechnology, 22, 292001.

Kaushik, C., Tuteja, R., Kaushik, N., Sharma, J. 2009. Minimization of organic chemical load in direct dyes effluent using low cost adsorbents. Chemical Engineering Journal, 155, 234-240.

Li, Z., Roy, S. J., Zou, Y., Bowman, R. S. 1998. Long-term chemical and biological stability of surfactant-modified zeolite. Environmental Science and Technology, 32, 2628-2632.

Li, R., Song, X., Huang, Y., Fang, Y., Jia, M., Ma, W. 2016. Visible-light photocatalytic degradation of azo dyes in water by Ag3PO4: An unusual dependency between adsorption and the degradation rate on pH value. Journal of Molecular Catalysis A: Chemical, 421, 57-65.

Li, Z., Bowman, R. S. 2001. Regeneration of surfactant-modified zeolite after saturation with chromate and perchloroethylene. Water Research, 35, 322-326.

Li, Z., Alessi, D., Allen, L. 2002. Influence of quaternary ammonium on sorption of selected metal cations onto clinoptilolite zeolite. Journal Of Environmental Quality, 31, 1106-1114.

Malek, N. A. N. N., Ramli, N. I. A. 2015. Characterization and antibacterial activity of cetylpyridinium bromide (Cpb) immobilized on kaolinite with different Cpb Loadings. Applied Clay Science, 109, 8-14.

Malek, N. A. N. N., Williams, C. D., Dhanabal, S., Bhall, H. S., Ibrahim, N. 2014. Natural clinoptilolite and chabazite as carrier for antibacterial agents of cetylpyridinium chloride (Cpc) and silver. Applied Mechanics And Materials. Trans Tech Publications, 29-33.

Mi-Na, Z., Xue-Pin, L., Bi, S. 2006. Adsorption of surfactants on chromium leather waste. Journal-Society of Leather Technologists and Chemists, 90, 1.

Negin, C., Ali, S., & Xie, Q. 2017. Most common surfactants employed in chemical enhanced oil recovery. Petroleum, 3(2), 197–211.

Onundi, Y. B., Mamun, A., Al Khatib, M., Al Saadi, M., Suleyman, A. 2011. Heavy metals removal from synthetic wastewater by a novel nano-size composite adsorbent. International Journal of Environmental Science & Technology, 8, 799-806.

Qiu, M., Qian, C., Xu, J., Wu, J., Wang, G. 2009. Studies on the adsorption of dyes into clinoptilolite. Desalination, 243, 286-292.

Patel, K., Singh, N., Nayak, J. M., Jha, B., Sahoo, S. K., Kumar, R. 2018. Environmentally friendly inorganic magnetic sulfide nanoparticles for efficient adsorption-based mercury remediation from aqueous solution. Chemistry Select, 3, 1840–1851.

Sadon, F., Ibrahem, A. S., Ismail, K. N. 2012. An overview of rice husk applications and modification techniques in wastewater treatment. Journal of Purity, Utility Reaction and Environment, 1, 308-334.

Sadegh, H., Ali, G. A. M., Gupta, V. K., Makhlouf, A. S. H., Shahryari-ghoshekandi, R., Nadagouda, M. N., Megiel, E. 2017. The role of nanomaterials as effective adsorbents and their applications in wastewater treatment. Journal of Nanostructure in Chemistry, 7(1), 1–14.

Tijani, N., Ahlafi, H., Smaihi, M., El Mansouri, A. 2013. Preparation and characterization of NaA zeolite membranes and its application for removal of heavy metals. Mediterranean Journal of Chemistry, 2, 484-492.

Torres-Pérez, J., Solache-Ríos, M., Colín-Cruz, A. 2008. Sorption and desorption of dye remazol yellow onto a mexican surfactant-modified clinoptilolite rich tuff and a carbonaceous material from pyrolysis of sewage sludge. Water, Air, and Soil Pollution, 187, 303-313.

Vassileva, P., Voikova, D. 2009. Investigation on natural and pretreated bulgarian clinoptilolite for ammonium ions removal from aqueous solutions. Journal of Hazardous Materials, 170, 948-953.

Vojoudi, H., Badiei, A., Bahar, S., Ziarani, G. M., Faridbod, F., Ganjali,M. R. 2017. A new nano-sorbent for fast and efficient removal of heavy metals from aqueous solutions based on modification of magnetic mesoporous silica nanospheres. Journal of Magnetism and Magnetic Materials, 441, 193-203.

Yang, L., Ma, X., Guo, N. 2012. Sodium alginate/Na+-rectorite composite microspheres: preparation, characterization, and dye adsorption. Carbohydrate Polymers, 90, 853-8.

Yusof A. M., Malek N. A. N. N. 2008. Removal of Cr(VI) and As(V) from aqueous solutions by HDTMA-modified zeolite Y. Journal of Hazardous Materials, 162, 1019–1024.

Zhu, J., Zhu, Y., Zhu, L., Rigutto, M., Van Der Made, A., Yang, C., Pan, S., Wang, L., Zhu, L., Jin, Y. 2014. Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template. Journal of the American Chemical Society, 136, 2503-2510.