Kinetic and thermodynamic studies on Methylene Blue biosorption by Algerian Olive Stone

K. Batouche, M. Chikhi, F. Balaska, A. Abbaz


Abstract: Equilibrium adsorption isotherm for the removal of basic dye Methylene Blue (MB) from aqueous solution using olive stone (OS) has been investigated. Equilibrium data were mathematically modelled using the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin adsorption models to describe the equilibrium isotherms and isotherm constants were determined. The results indicate the potential use of the adsorbent to remove MB from the aqueous solution. Maximum adsorption capacity of 2.6 mg.g-1 was reached at equilibrium. The Temkin isotherm was found to better fit the correlation coefficient of the experimental data (R2> 0.97). Pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models were used to study the kinetic data. The results showed that the intraparticle diffusion model was the best one with R2=1 followed by the pseudo-second-order kinetic model. Characteristics of adsorption were determined as spontaneous for ΔG°≤-3.4 kJ.mol-1 and endothermic for ΔH° value of 2.8 kJ.mol-1. The findings obtained suggest that olive stones are a desirable candidate as low-cost biomaterial for extracting simple dye MB from aqueous solutions.

Full Text:



Kumar, K.; Vasanth, V.; Ramamurthi, Sivanesan, S. Modeling the mechanism involved during the sorption of methylene blue onto fly ash." Journal of colloid and interface science 284.1 (2005) 14-21.

Banat, F.; Al-Asheh, S.; Al-Ahmad, R.; Bni-Khalid, F. Bench-scale and packed bed sorption of methylene blue using treated olive pomace and charcoal. Bioresource technology 98.16 (2007) 3017-3025.

Cao, J. S.; Lin, J. X.; Fang, F.; Zhang, M. T.; Hu, Z. R. A new absorbent by modifying walnut shell for the removal of anionic dye: kinetic and thermodynamic studies. Bioresource technology 163 (2014) 199-205.

Semeraro, P. ; Rizzi, V. ; Fini, P. ; Matera, S. ; Cosma, P. ; Franco, E.; ... Fortea, I. Interaction between industrial textile dyes and cyclodextrins. Dyes and Pigments 119 (2015) 84-94.

Bulut, Y.; Aydın, H. A kinetics and thermodynamics study of methylene blue adsorption on wheat shells. Desalination 194.1-3 (2006) 259-267.

Albadarin, A. B.; Mo, J.; Glocheux, Y.; Allen, S.; Walker, G.; Mangwandi, C. Preliminary investigation of mixed adsorbents for the removal of copper and methylene blue from aqueous solutions. Chemical engineering journal 255 (2014) 525-534.

Ari, A. G.; Celik, S. Biosorption potential of Orange G dye by modified Pyracanthacoccinea: Batch and dynamic flow system applications. Chemical engineering journal 226 (2013) 263-270.

Khataee, A. R.; Vafaei, F.; Jannatkhah, M. Biosorption of three textile dyes from contaminated water by filamentous green algal Spirogyra sp.: Kinetic, isotherm and thermodynamic studies. International Biodeterioration & Biodegradation 83 (2013) 33-40.

Kabbout, Rana, and Samir Taha. Biodecolorization of textile dye effluent by biosorption on fungal biomass materials. Physics Procedia 55 (2014): 437-444.

Albadarin, A. B.; Mangwandi, C.; Walker, G. M.; Allen, S. J.; Ahmad, M. N. Biosorption characteristics of sawdust for the removal of Cd (II) ions: mechanism and thermodynamic studies. Chem. Eng. Trans 24 (2011) 1297-1302.

Abdolali, A.; Guo, W. S.; Ngo, H. H.; Chen, S. S.; Nguyen, N. C.; Tung, K. L. Typical lignocellulosic wastes and by-products for biosorption process in water and wastewater treatment: a critical review. Bioresourcetechnology 160 (2014) 57-66.

Guerrero-Coronilla, I.; Morales-Barrera, L.; Cristiani-Urbina, E. Kinetic, isotherm and thermodynamic studies of amaranth dye biosorption from aqueous solution onto water hyacinth leaves. Journal of environmental management 152 (2015) 99-108.

Magriotis, Z. M.; Vieira, S. S.; Saczk, A. A.; Santos, N. A.; Stradiotto, N. R. Removal of dyes by lignocellulose adsorbents originating from biodiesel production. Journal of Environmental Chemical Engineering 2.4 (2014) 2199-2210.

Wang, M. X.; Zhang, Q. L.; Yao, S. J. A novel biosorbent formed of marine-derived Penicilliumjanthinellum mycelial pellets for removing dyes from dye-containing wastewater. Chemical Engineering Journal 259 (2015) 837-844.

Fiol, N.; Villaescusa, I.; Martinez, M.; Miralles, N.; Poch, J.; Serarols, J. Biosorption of Cr (VI) using low cost sorbents. Environmental Chemistry Letters 1.2 (2003) 135-139.

Calero, M., Hernáinz, F., Blázquez, G., Martín-Lara, M. A., Tenorio, G. Biosorption kinetics of Cd (II), Cr (III) and Pb (II) in aqueous solutions by olive stone. Brazilian Journal of Chemical Engineering 26.2 (2009) 265-273.

Hodaifa, G.; Ochando-Pulido, J. M.; Alami, S. B. D.; Rodriguez-Vives, S.; Martinez-Ferez, A. Kinetic and thermodynamic parameters of iron adsorption onto olive stones. Industrial crops and products 49 (2013) 526-534.

Soufi, O. ; Romero, C.; Louaileche, H. Ortho-diphenol profile and antioxidant activity of Algerian black olive cultivars: Effect of dry salting process. Food chemistry 157 (2014) 504-510.

ITAFV. (2011). Technical Institute of Fruit and Vine Arboriculture. Table olives statistics 2011. Study Department General Direction (Algiers)

Albadarin, A. B., Mangwandi, C. Mechanisms of Alizarin Red S and Methylene blue biosorption onto olive stone by-product: Isotherm study in single and binary systems. Journal of environmental management 164 (2015) 86-93.

Trujillo, M. C.; Martín-Lara, M. A.; Albadarin, A. B., Mangwandi, C.; Calero, M. Simultaneous biosorption of methylene blue and trivalent chromium onto olive stone. Desalination and Water Treatment 57.37 (2016) 17400-17410.

Lagergren, S. About the theory of so-called adsorption of soluble substances, Kungliga Svenska Vetenskapsakademiens Handlingar 24 (1898) 1–39, as cited by HC Trivedi, M. Patel, RD Patel, Adsorption of cellulose triacetate on calcium silicate. J. Eur. Polym. 9 (1973) 525-531.

Ho, Y. S.; McKay, G. Pseudo-second order model for sorption processes. Process biochemistry 34.5 (1999) 451-465.

Weber, W. J.; Morris, J. C. Kinetics of adsorption on carbon from solution. Journal of the sanitary engineering division 89.2 (1963) 31-60.

Zeldowitsch, J. Über den mechanismus der katalytischenoxydation von CO an MnO2. Actaphysicochim. URSS 1 (1934): 364-449.

Chien, S. H.; Clayton, W. R. Application of Elovich equation to the kinetics of phosphate release and sorption in soils 1. Soil Science Society of America Journal 44.2 (1980) 265-268.

Sparks, D. L. Kinetics of reaction in pure and mixed systems. Soil physical chemistry 44 (1986) 265-268.

Langmuir, I. The adsorption of gases on plane surfaces of glass, mica and platinum. Journal of the American Chemical society 40.9 (1918) 1361-1403.

Freundlich, H. M. F. Over the adsorption in solution. J. Phys. Chem 57.385471 (1906) 1100-1107.

Dubinin, M. M. The equation of the characteristic curve of activated charcoal. Dokl.Akad.Nauk. SSSR 55 (1947) 327-329

Temkin, M. I. Kinetics of ammonia synthesis on promoted iron catalysts. Actaphysiochim. URSS 12 (1940) 327-356.

Tan, C. Y.; Li, M.; Lin, Y. M.; Lu, X. Q.; Chen, Z. L. Biosorption of Basic Orange from aqueous solution onto dried A. filiculoides biomass: Equilibrium, kinetic and FTIR studies. Desalination 266.1-3 (2011) 56-62.

Weber, T. W.; Chakravorti, R. K. Pore and solid diffusion models for fixed‐bed adsorbers. AIChE Journal 20.2 (1974) 228-238.

Ghasemi, M.; Mashhadi, S.; Asif, M., Tyagi, I.; Agarwal, S.; Gupta, V. K. Microwave-assisted synthesis of tetraethylenepentamine functionalized activated carbon with high adsorption capacity for Malachite green dye. Journal of Molecular Liquids 213 (2016) 317-325.

Rieman, W.; Walton, H. F. Ion exchange in analytical chemistry: international series of monographs in analytical chemistry. Elsevier (2013).

Biswas, K.; Saha, S. K.; & Ghosh, U. C. Adsorption of fluoride from aqueous solution by a synthetic iron (III) aluminum (III) mixed oxide." Industrial& Engineering Chemistry Research 46.16 (2007) 5346-5356.

Ahmad, M. A.; Ahmad, N.; Bello, O. S. Modified durian seed as adsorbent for the removal of methyl red dye from aqueous solutions. Applied Water Science 5.4 (2015) 407-423.

Bhattacharyya, K. G.; Sharma, A. Kinetics and thermodynamics of methylene blue adsorption on neem (Azadirachtaindica) leaf powder. Dyes and pigments 65.1 (2005) 51-59.

Franca, A. S.; Oliveira, L. S.; Ferreira, M. E. Kinetics and equilibrium studies of methylene blue adsorption

by spent coffee grounds. Desalination 249.1 (2009) 267-272.

Han, R.; Zhang, J.; Han, P.; Wang, Y.; Zhao, Z.; Tang, M. Study of equilibrium, kinetic and thermodynamic parameters about methylene blue adsorption onto natural zeolite. Chemical Engineering Journal 145.3 (2009) 496-504.

Chakrabarti, S.; Dutta, B. K. On the adsorption and diffusion of methylene blue in glass fibers. Journal of colloid and interface science 286.2 (2005) 807-811.

Shawabkeh, R. A.; Tutunji, M. F. Experimental study and modeling of basic dye sorption by diatomaceous clay. Applied Clay Science 24.1-2 (2003) 111-120.

Ghosh, D.; Bhattacharyya, K. G. Adsorption of methylene blue on kaolinite. Applied clay science 20.6 (2002) 295-300.

Fu, Y.; Viraraghavan, T. Removal of a dye from an aqueous solution by the fungus Aspergillus niger. Water Quality Research Journal 35.1 (2000) 95-111.

Batzias, F.; Sidiras, D.; Schroeder, E.; Weber, C. Simulation of dye adsorption on hydrolyzed wheat straw in batch and fixed-bed systems. Chemical Engineering Journal 148.2-3 (2009) 459-472.

Lee, C. K.; Low, K. S.; Chow, S. W. Chrome sludge as an adsorbent for colour removal. Environmental technology 17.9 (1996) 1023-1028.

Woolard, C. D.; Strong, J.; Erasmus, C. R. Evaluation of the use of modified coal ash as a potential sorbent for organic waste streams. Applied Geochemistry 17.8 (2002) 1159-1164.

Tsai, W. T.; Yang, J. M.; Lai, C. W.; Cheng, Y. H.; Lin, C. C.; Yeh, C. W. Characterization and adsorption properties of eggshells and eggshell membrane. Bioresource technology 97.3 (2006) 488-493.

Mak, S. Y.; Chen, D. H. Fast adsorption of methylene blue on polyacrylic acid-bound iron oxide magnetic nanoparticles. Dyes and pigments 61.1 (2004) 93-98.

Ahmad, A. A., Hameed, B. H.; Aziz, N. Adsorption of direct dye on palm ash: Kinetic and equilibrium modeling. Journal of hazardous materials 141.1 (2007) 70-76.

Annadurai, G.; Juang, R. S.; Lee, D. J. Use of cellulose-based wastes for adsorption of dyes from aqueous solutions. Journal of hazardous materials 92.3 (2002) 263-274.

Cheung, W. H.; Szeto, Y. S.; McKay, G. Intraparticle diffusion processes during acid dye adsorption onto chitosan. Bioresource technology 98.15 (2007) 2897-2904.

Sepehr, M.N.; Amrane, A.; Karimaian, K. A.; Zarrabi, M.; Ghaffari, H. R. Potential of waste pumice and surface modified pumice for hexavalent chromium removal: Characterization, equilibrium, thermodynamic and kinetic study. Journal of the Taiwan Institute of Chemical Engineers 45.2 (2014) 635-647.

Ahmad, M. A.; Puad, N. A. A.; Bello, O. S. Kinetic, equilibrium and thermodynamic studies of synthetic dye removal using pomegranate peel activated carbon prepared by microwave-induced KOH activation. Water Resources and industry 6 (2014) 18-35.

Ahmed, M. J. Application of agricultural based activated carbons by microwave and conventional activations for basic dye adsorption. Journal of Environmental Chemical Engineering 4.1 (2016) 89-99.

Ahmed, M. J. Preparation of activated carbons from date stones by chemical activation method using FeCl3 and ZnCl2 as activating agents. Journal of Engineering 17.4 (2011) 1007-1022.

Bello, O. S.; Ahmad, M. A.; Ahmad, N. Adsorptive features of banana (Musa paradisiaca) stalk-based activated carbon for malachite green dye removal. Chemistry and Ecology 28.2 (2012) 153-167.

Bello, O. S.; Fatona, T. A.; Falaye, F. S.; Osuolale, O. M.; Njoku, V. O. Adsorption of eosin dye from aqueous solution using groundnut hull–based activated carbon: kinetic, equilibrium, and thermodynamic studies. Environmental Engineering Science 29.3 (2012) 186-194.

Baek, M.H.; Ijagbemi, C.O.; Se-Jin, O.; Kim, D. S. Removal of Malachite Green from aqueous solution using degreased coffee bean. Journal of hazardous materials 176.1-3 (2010) 820-828.

Önal, Y.; Akmil-Başar, C.; Eren, D.; Sarıcı-Özdemir, Ç.; Depci, T. Adsorption kinetics of malachite green onto activated carbon prepared from Tunçbilek lignite. Journal of hazardousmaterials 128.2-3 (2006) 150-157.


  • There are currently no refbacks.