Preparation of Clay Minerals – Natural Surfactant Composites to Remove Organic Dyes and Heavy Metals

Livy Laysandra, Darwin Kurniawan, Felycia Edi Soetaredjo, Suryadi Ismadji


The rapid development of industry is considered to be the main cause of various environmental problems, which are mainly caused by the discharge of wastewater which contains many hazardous compounds. Dyes and heavy metals are type of hazardous substances that are often found in industrial wastewater and cause ecosystem damage. Dyes and heavy metals are more difficult to remove due to their inability to be broken down, so they can build up and reach dangerous levels. Adsorption is a straighforward and efficient method for dealing with hazardous substance contamination in water. Clay minerals, known for their efficient adsorption properties, were chosen for this procedure. Clay minerals are porous materials so they are suitable for use as adsorbents. The intercalation technique is a robust strategy to further increase the adsorption capacity of clay minerals, which is done by treating clay minerals with surfactants. Clay minerals modified with natural surfactants are considered as a potential choice for removal procedures. The use of this natural surfactant was chosen because of its excellent adsorption capacity and environmentally friendly properties. Polar lipids, natural surfactants, are commonly present in the lipid layers of plants and animals. This review focuses on the synthesis of modified clay minerals using different natural surfactants such as soybeans, saponins, lipopeptides, and rhamnolipids, as well as the use of alternative clay mineral/natural surfactant composites. This review describe various types of natural surfactants that can be used to modify clay minerals and their application in the adsorption process.

Save to Mendeley


Natural surfactant; Clay mineral; Modification; Adsorption; Application

Full Text:



Crini, G. 2006, "Non-Conventional Low-Cost Adsorbents for Dye Removal: A Review." Biores Technol, 97, 1061-1085.

Yang, M. 2011, "A current global view of environmental and occupational cancers." J Environ Sci Health Part. C, 29, 223-249.

Volesky, B., Holan, Z.R. 1995, "Biosorption of Heavy Metals." Biotechnol Prog, 11, 235–250.

Qaiser, S., Saleemi, A.R., Ahmad, M.M. 2007, "Heavy metal uptake by agro based waste materials." Environ Biotechnol, 10, 409–41.

Peternele, W.S., Winkler-Hechenleitner, A.A., Gomez Pineda, E.A. 1999, "Adsorption of Cd(II) and Pb(II) onto functionalized formic lignin from sugar bagasse." Biores Technol 68, 95–100.

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." Chem Eng J, 189– 190, 264– 274.

Hu, Q.H., Qiao, S.Z., Haghseresht, F., Wilson, M.A., Lu, G.Q. 2006, "Adsorption study for removal of basic red dye using bentonite." Ind Eng Chem Res, 45, 733-738.

Alther, G.R. 2002, "Using organo clays to enhance carbon filtration." Waste Manag, 22, 507–513.

Lang, S., Wagner, F. "Structure and properties of biosurfactants." In: Biosurfactants and Biotechnology (Kosaric N, Cairns WL, Gray NCC, eds). New York:Marcel Dekker, 1987;21-45

Fiechter A. 1992, "Biosurfactants: moving towards industrial application." Trends Biotech, 10, 208-217.

wang, L., Wang, A. 2008, "Adsorption properties of Congo Red from aqueous solution onto surfactant-modified montmorillonite." J Hazard Mater, 160, 173–180.

Jaynes, W.F., Boyd, S.A. 1991, "Hydrophobicity of siloxane surfaces in smectites as revealed by aromatic hydrocarbon adsorption from water." Clays Clay Miner, 39, 428–436.

Rutherford, D.W., Chiou, C.T. 1992, "Effect of water saturation in soil organic matter on the partition of organic compounds." Environ Sci Technol, 26, 965–970.

Smith, J.A., Bartelt-Hunt, S.L., Susan, E. "Sorption and permeability of gasoline hydrocarbons in organobentonite porous media." J Hazard Mater B96, 91–97.

Holmberg, K. 2001. Curr Opin Colloid Interface Sci, 6, 148159.

Mulligan, C.N. 2009, "Recent advances in the environmental applications of biosurfactants." Curr Opin Colloid Interface Sci, 14, 372–378.

Urum, K., Pekdemir, T. 2004, "Evaluation of biosurfactants for crude oil contaminated soil washing." Chemosphere, 57, 1139–1150.

Holmberg, K. 2001, "Natural surfactants." Curr. Opin. Colloid Interface Sci, 6, 148–159.

Rodrigues, L., Banat, I.M., Teixeira, J., Oliveira, R. 2006, "Biosurfactants: Potential applications in medicine." J Antimicrob Chem, 57, 609–618.

Merino, D., Ollier, R., Lanfranconi, M., Alvarez, V. 2016, "Preparation and characterization of soy lecithin-modified bentonites.' Appl Clay Sci, 127–128, 17–22.

Oleszek, W., Hamed, A. 2010, Saponin-based surfactants, In Surfactants from renewable resources, Wiley Series in Renewable Resources, Kjellin, M. & Johansson, I. (Ed.), 239- 252, Wiley, ISBN: 978-0-470-76041-3, West Sussex.

Dickinson, E. 1993, "Towards more natural emulsifiers." Trends Food Sci Tech, 4, 330-334.

Garti, N. (2002). Food emulsifiers: structure-reactivity relationships, design, and applications, In: Physical properties of lipids, Marangoni, A. G. & Narine, S. (Ed.), 265-386, Marcel Dekker, Inc., ISBN: 978-0-8247-0005-8, New York.

Merino, D., Ollier, R., Lanfranconi, M., Alvarez, V. 2016, "Preparation and characterization of soy lecithin-modified bentonites." Appl Clay Sci 127–128, 17–22.

Wicklein, B., Darder, M., Aranda, P., Ruiz-Hitzky, E. 2010, "Bio-organoclays based on phospholipids as immobilization hosts for biological species." Langmuir 26, 5217–5225.

Ludueña, L.N., Vazquez, A., Alvarez, V.A. 2013, "Effect of the type of clay organo-modifier on the morphology, thermal/mechanical/impact/barrier properties and biodegradation in soil of polycaprolactone/clay nanocomposites." J Appl Polym Sci, 128, 2648–2657.

Nagy, K., Bíró, G., Berkesi, O., Benczédi, D., Ouali, L., Dékány, I. 2013, "Intercalation of lecithins for preparation of layered nanohybrid materials and adsorption of limonene." Appl Clay Sci, 72, 155–162.

Sparg, S.G., Light, M.E., van Staden, J.J. 2004, "Biological activities and distribution of plant saponins." Ethnopharmacol, 94, 219-243.

Ouellet-Plamondon, C.M., Stasiak, J., Al-Tabbaa, A. 2014, "The effect of cationic, non-ionic and amphiphilic surfactants on the intercalation of bentonite." Colloids Surfaces A Physicochem Eng Asp, 444, 330–337.

Wicklein, B., Darder, M., Aranda, P., Ruiz-hitzky, E. 2010, “Bio-organoclays Based on Phospholipids as Immobilization Hosts for Biological Species.” Langmuir, 26, 5217-5225.

Luduena, L.N., Vasquez, A., Alvarez, V.A. 2013, "Effect of the Type of Clay Organo-Modifier on the Morphology, Thermal/Mechanical/Impact/Barrier Properties and Biodegradation in Soil of Polycaprolactone/Clay Nanocomposites." J App Polym Sci, 38425.

Nagy, K., Biro, G., Benczédi, D., Ouali, L., Dékány, I. 2013, "Intercalation of lecithins for preparation of layered nanohybrid materials and adsorption of limonene" Appl Clay Sci, 72, 155–162.

Sparg, S.G., Light, M.E., van Staden, J. 2004, "Biological activities and distribution of plant saponins." J Ethnopharmacolog, 94, 219-243.

Cheeke, P.R. 2001, "Actual and potential applications of Yucca schidigera and Quillaja saponaria saponins in human and animal nutrition ." Recent Adv Anim Nutri Australia 13, 115-126.

Cowan, M.M. 1999, "Plant Products as Antimicrobial Agents." Clinical Microbiol Rev, 12, 564-582.

Cares, M.G., Vargas, Y., Gaete, L., Sainz, J., Alarcón, J. 2010, "Ultrasonically assisted Extraction of bioactive principles from Quillaja Saponaria Molina." Phys. Procedia, 3, 169–178.

Vincken, J.P., Heng, L., de Groot, A. and Gruppen, H. 2007, “Saponins, Classification and Occurrence in the Plant Kingdom.” Phytochem, 68, 275-297.

Van Setten, D.C., Jan Ten Hove, G., Wiertz, E.J.H.J., Kamerling, J.P., Van De Werken, G. 1998, "Multiple-stage tandem mass spectrometry for structural characterization of saponins." Anal Chem, 70, 4401–4409.

Nord, L.I., Kenne, L. 1999, "Separation and structural analysis of saponins in a bark extract from Quillaja saponaria Molina." Carbohydr Res, 320, 70-81.

Vinatoru, M. 2001, "An Overview of the Ultrasonically Assisted Extraction of Bioactive Principles from Herbs." Ultrasonics Sonochem, 8, 303-313.

Wang, L. and Weller, C.L. 2006, "Recent Advances in Extraction of Nutraceuticals from Plants." Trends Food Sci Technol, 17, 300-312.

Gaete-Garretón, L., Vargas-Hernández, Y., Cares-Pacheco, M.G., Sainz, J., Alarcón, J. 2011, "Ultrasonically enhanced extraction of bioactive principles from Quillaja Saponaria Molina." Ultrasonics, 51, 581-585.

Gusiatin, Z.M. Klimiuk, E. 2012, "Metal (Cu, Cd and Zn) removal and stabilization during multiple soil washing by saponin." Chemosphere, 86, 383–391.

Hong, K.J., Tokunaga, S., Kajiuchi, T. 2002, "Evaluation of remediation process with plant-derived biosurfactant for recovery of heavy metals from contaminated soils." Chemosphere, 49, 379–387.

Zhan, H., Jiang, Y., Wang, B., Zhu, K., Zhao, B. 2008, "Study on removal efficiencies and mechanism of heavy metal from sewage irrigated soils by saponin compared with commonly used washing agents." Int J Sci Eng Res, 3, 461-469.

Kurniawan, A., Sutiono, H., Ju, Y.H., Soetaredjo, F.E., Ayucitra, A., Yudha, A., Ismadji, S. 2011," Utilization of rarasaponin natural surfactant for organo-bentonite preparation: Application for methylene blue removal from aqueous effluent." Microporous Mesoporous Mater, 142, 184–193.

Chandra, I.K., Ju, Y.H., Ayucitra, A., Ismadji, S. 2013, "Evans blue removal from wastewater by rarasaponin–bentonite." Int J Environ Sci Technol, 10, 359–370.

Schmitt, C., Grassi, B., Lespes, G., Desbrières, J., Pellerin, V., Reynaud, S., Gigault, J., Hackley, V.A. 2014, "Saponins: A Renewable and Biodegradable Surfactant From Its Microwave-Assisted Extraction to the Synthesis of Monodisperse Lattices." Biomacromolecules, 15, 856–862.

Zhou, W., Wang, X., Chen, C., Zhu, L. 2013, "Enhanced soil washing of phenanthrene by a plant-derived natural biosurfactant, Sapindus saponin." Colloids Surfaces A Physicochem Eng Asp, 425, 122–128.

Chtioui, O., Dimitrov, K., Gancel, F., Nikov, I. 2010, "Biosurfactants production by immobilized cells of Bacillus subtilis ATCC 21332 and their recovery by pertraction." Process Biochem, 45, 1795–1799.

Wei, Y., Wang, L. Chang, J. 2004, "Optimizing Iron Supplement Strategies for Enhanced Surfactin Production with Bacillus subtilis." Biotechnol Progress, 20, 979–983.

58. Tsuji, G. Y., Hoogenboom, G., & Thornton, P. K. 1998. Understanding Options for Agricultural Production. Berlin: Springer.

Zhu, Z., Zhang, G., Luo, Y., Ran, W., Shen, Q. 2012, "Production of lipopeptides by Bacillus amyloliquefaciens XZ-173 in solid state fermentation using soybean flour and rice straw as the substrate." Bioresour Technol 112, 254–260.

Zhu, Z., Gao, C., Wu, Y., Sun, L., Huang, X., Ran, W., Shen, Q. 2013, "Removal of heavy metals from aqueous solution by lipopeptides and lipopeptides modified Na-montmorillonite." Bioresour Technol, 147, 378–386.

Abdel-Mawgoud, A.M., Aboulwafa, M.M., Hassouna, N.A.H. 2009, "Characterization of Rhamnolipid Produced by Pseudomonas aeruginosa Isolate Bs20." Appl Biochem Biotechnol, 157, 329–345.

Wang, S., Mulligan, C.N. 2004, "An evaluation of surfactant foam technology in remediation of contaminated soil." Chemosphere, 57, 1079–1089.

Helvac, S.S., Peker, S., Özdemir, G. 2004, "Effect of electrolytes on the surface behavior of rhamnolipids R1 and R2." Colloids Surf B Biointerfaces, 35, 225–233.

Nurbas, M. 2010, "Investigation of sorption/desorption equilibria of heavy metal ions on/from quartz using rhamnolipid biosurfactant." J Env Manag, 91, 724–731.

Taqvi, S.I.H., Hasany, S.M., Bhanger, M.I. 2007, "Sorption profile of Cd (II) ions onto beach sand from aqueous solutions." J Hazard Mater, 141, 37–44.

Ozturk, B., Argin, S., Ozilgen, M., McClements, D.J. 2014, "Formation and stabilization of nanoemulsion-based vitamin E delivery systems using natural surfactants: Quillaja saponin and lecithin." J Food Eng, 142, 57–63.

Park, J.K., Bin Choy, Y., Oh, J.M., Kim, J.Y., Hwang, S.J., Choy, J.H. 2008, "Controlled release of donepezil intercalated in smectite clays." Int J Pharm, 359, 198–204.

Calabrese, I., Gelardi, G., Merli, M., Liveri, M.L.T., Sciascia, L. 2017, "Clay-biosurfactant materials as functional drug delivery systems: Slowing down effect in the in vitro release of cinnamic acid." Appl Clay Sci, 135, 567–574.

Wiesner, J., Mitsch, A., Wissner, P., Jomaa, H., Schlitzer, M. 2001, "Structure–activity relationships of novel anti-malarial agents. Part 2: cinnamic acid derivatives." Bioorg Med Chem Lett, 11, 423–424.

Moslemizadeh, A., Khezerloo-ye Aghdam, S., Shahbazi, K., Zendehboudi, S. 2017, "A triterpenoid saponin as an environmental friendly and biodegradable clay swelling inhibitor." J Mol Liq, 247, 269–280.

Bahmani, M., Rafieian-Kopaei, M., Jeloudari, M., Eftekhari, Z., elfan, B., Zargaran, A., Forouzan, S. 2014, "A review of the health effects and uses of drugs of plant licorice (Glycyrrhiza glabra L.) in Iran." Asian Pacific J Trop Dis, 4, S847–S849.

ShamsiJazeyi, H., Verduzco, R., Hirasaki, G.J. 2014, “Reducing adsorption of anionic surfactant for enhanced oil recovery: Part II. Applied aspects.” Colloids Surfaces A Physicochem Eng Asp, 453, 168–175.

Lovaglio, R.B., dos Santos, F.J., Jafelicci, M., Contiero, J. 2011, “Rhamnolipid emulsifying activity and emulsion stability: pH rules.” Colloids Surfaces B Biointerfaces 85 (2011) 301–305.